Multifunctional polymers

ABSTRACT

Described herein are multifunctional polymers comprising a first repeating unit having at least one pseudo-cationic moiety, a second repeating unit having at least a hydrophobic moiety, and a third repeating unit, where the weight-average molecular weight is less than about 10,000 Da. In one embodiment the polymers exhibit antimicrobial activity. Also provided are compositions formulated with the multifunctional polymers, and a method of providing antimicrobial activity.

BACKGROUND Field of the Invention

The invention provides multifunctional polymers comprising a repeat unithaving a pseudo-cationic moiety, a repeat unit having a hydrophobicmoiety, and a third repeat unit. In one embodiment the polymer has aweight-average molecular weight of less than about 10,000 Da. In anotherembodiment the polymers exhibit antimicrobial activity. The polymers maybe prepared by known polymerization methods, such as radical orcondensation polymerization. Depending upon the repeating unit types andratios, the resulting polymers can have a wide variety of physical andchemical properties. The multifunctional polymers of the invention canbe employed in a wide variety of compositions. Also disclosed is amethod of providing antimicrobial activity through the use of themultifunctional polymers.

Description of Related Art

Antimicrobial compounds are widely used in many formulations, where theymay assist in killing or inhibiting the growth and presence of microbesas bacterium, fungus, or protozoan, or combinations thereof. In thepersonal care arts antimicrobial compounds may be called“preservatives,” while in non-personal care applications-such asadhesives, coatings, inks, membranes, textiles, and paints-antimicrobialcompounds may be called “biocides.” Regardless, regulatory andenvironmental concerns have put limits on the selection and usage oftraditional preservatives. Non-traditional antimicrobial compounds, suchas multifunctional polymers, have attracted much attention in thechemical industry. Antimicrobial polymers are nonvolatile, do notpenetrate the skin, have better long-term efficiency and possibly higherselectivity compared to traditional preservatives. Antimicrobialpolymers also minimize environmental problems by minimizing residualtoxicity.

Multifunctional polymers are described in the following disclosures,each of which is incorporated herein by reference. De Grado, et al., inJ. Am. Chem. Soc., 2005, 127, 4128, and U.S. Pat. Appl. No. 2006/0024264disclose the synthesis and uses of amphiphilic polymethacrylatederivatives as antimicrobial agents. Kuroda, et al., in Chem. Eur. J. ,2009, 15, 1123, describes the role of hydrophobicity in theantimicrobial and hemolytic activities of polymethacrylate derivatives.Gellman, et al., in Org. Lett., 2004, 4, 557, discloses the biocidalactivity of polystyrene derivatives bearing cationic properties throughreversible amine protonation. U.S. Pat. No. 6,214,885 describes the useof polymers containing β-hydroxyalkylvinylamine units as biocides. U.S.Pat. No. 5,208,016 discloses antimicrobial resin compositions containingethylene copolymer from radical polymerization of ethylene anddialkylaminoalkylacrylamide co-repeating units.

Other references related to these polymers include the following patentsand patent applications: EP 40,498; GB 686,381; 730,463; 870,398;922,878; 1,286,966; 1,329,033; JP 53,090,397; 57,161,859; U.S. Pat. Nos.3,449,250; 3,555,001; 4,048,422; 4,058,491; 4,734,446; 4,767,616;5,229,458; 5,352,729; 5,408,022; 5,449,775; 5,492,988; 5,756,181;6,025,501; 6,071,993; 6,075,107; 6,299,866; 6,646,082; 6,682,725;6,737,049; 6,838,078; 6,951,598; 7,033,607; 7,041,281; 7,323,163;7,326,262; 7,592,040; 7,955,594; US 2005/0152855; 2006/0024264;2007/0082196; 2007/0161519; 2007/0238807; 2009/0029129; 2009/0312214;2010/00029838; 2010/00298504; 2010/0130678; 2010/0137455; 2010/0174040;2011/0060166, and WO 2010/0014655; 2010/031144 and PCT/U513/030115.

Accordingly, there is a need for multifunctional polymers to alter orimprove the physicochemical properties of such polymers.

SUMMARY

The invention provides polymers that are polymerized from (A) a firstrepeating unit A comprising at least one pseudo-cationic moiety, (B) asecond repeating unit B comprising at least one hydrophobic moiety, and(C) a third repeating unit C, and wherein the weight-average molecularweight of said polymer is less than about 10,000 Da. The polymer may bea terpolymer or comprise more than three repeating units. Additionally,the polymers may be synthesized via radical or condensationpolymerization techniques.

In one embodiment, the polymers may exhibit antimicrobial activity.

Also provided are compositions having one or more of the multifunctionalpolymers, as well as a method of providing antimicrobial activity.

DETAILED DESCRIPTION

Described herein are polymers that are polymerized from at least threerepeating unit types that are distinctly different from those known inthe related art. In one embodiment, the polymers may exhibitantimicrobial properties, such as being microbiocidal and/ormicrobiostatic, which may lend their use in any number of formulationsthat may benefit from this effect. As a non-limiting aspect of thisembodiment, the polymers may exhibit a broad spectrum of activityagainst many different types of microbes, including activity against S.aureus, E. coli, and P. aeruginosa. In another non-limiting aspect, thepolymers may be formulated into compositions.

As used herein, the following terms have the meanings set out below.

The term “microbe” refers to any bacterium, fungus, protozoan, and anycombination thereof.

The term “antimicrobial” refers to a substance that kills or inhibitsthe growth of microbes such as bacterium, fungus, or protozoan, orcombinations thereof. Antimicrobials may kill microbes (microbiocidal)and/or prevent the growth of microbes (microbiostatic). The term“antimicrobial activity” refers to activity that kills and/or inhibitsthe growth of one or more microbes.

The term “functionalized” refers to replacing one or more hydrogens withone or more non-hydrogen groups, for e.g., alkyl, alkoxy, cycloalkyl,alkenyl, cycloalkenyl, alkynyl, and/or aryl groups. Alkyl, alkenyland/or alkynyl groups include C₁-C₆₀, more particularly C₁-C₃₆, and mostparticularly C₁-C₁₈ groups. Cycloalkyl groups include cyclopentane,cyclohexane, cycloheptane, and the like. Alkoxy groups include methoxy,ethoxy, n-propoxy, isopropoxy, and the like. Aryl groups includebenzenes, naphthalenes (2 rings), anthracenes (3 rings), and the like.

The term “anion” refers to an ion with more electrons than protons,giving it a net negative charge.

The term “cation” refers to an ion with fewer electrons than protons,giving it a net positive charge.

The term “halogenated” refers to chloro, bromo, iodo and fluoro. In oneembodiment halogen may be bromo and/or chloro.

The term “branched and unbranched alkyl groups” refers to alkyl groupswhich may be straight chained or branched. The alkyl group may have from1 to about 18 carbon atoms, more particularly, from 1 to about 10 carbonatoms, and yet more particularly from 1 to about 6 carbon atoms.Branched groups include iso-propyl, tert-butyl, sec-butyl, and the like.

The term “hydrocarbyl” refers to straight-chain and/or branched-chaingroups comprising carbon and hydrogen atoms with optional heteroatom(s).Particularly, the hydrocarbyl group includes C₁-C₆₀, more particularlyC₁-C₃₆, and most particularly C₁-C₁₈ alkyl and alkenyl groups optionallyhaving one or more hetero atoms. The hydrocarbyl group may be mono-, di-or polyvalent.

The term “heteroatom” refers to oxygen, nitrogen, sulfur, silicon,and/or phosphorous. The heteroatom may be present as a part of one ormore functional groups on the hydrocarbyl chain and/or as a part of thehydrocarbyl chain itself. When the heteroatom is a nitrogen atom, thenitrogen atom may be present in the form of a quaternary amine.

The term “generic substituent(s)” refer(s) to substituent(s) such asR₁-R₆, and subscripts a, b, and c used and defined in the invention.

The term “amphiphilic” refers to a compound possessing both hydrophilic(water-loving, polar) and hydrophobic (lipophilic, fat-loving,non-polar) properties. Such compounds are also referred to asamphipathic.

The term “C1-C20 alkyl” refers to groups such as: methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,n-pentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl,2-ethylhexyl, n-nonyl, iso-nonyl, 2-propylheptyl, n-decyl, n-dodecyl,n-tridecyl, iso-tri-decyl, n-tetradecyl, n-hexydecyl, n-octadecyl andeicosyl.

The term “C1-C20 alkylene” refers to groups such as: methylene,ethylene, n-propylene, iso-propylene, n-butylene, iso-butylene,sec-butylene, tert-butylene, n-pentylene, sec-pentylene, tert-pentylene,n-hexylene, n-heptylene, n-octylene, 2-ethylhexylene, n-nonylene,iso-nonylene, 2-propylheptylene, n-decylene, n-dodecylene,n-tridecylene, iso-tri-decylene, n-tetradecylene, n-hexydecylene,n-octadecylene and eicosylene.

The term “pseudo-cationic moiety” refers to moiety comprising one ormore functionalized and unfunctionalized nitrogen or phosphorus.

The term “repeating unit” refers to a small molecule that chemicallybonds during polymerization to one or more repeating units of the sameor different kind to form a polymer.

The term “(meth)acrylate” refers to both methacrylate and acrylate.Similarly, the term “(meth)acrylamide” refers to both methacrylamide andacrylamide.

The term “polymer” refers to a large molecule (macromolecule) comprisingrepeating structural units polymerized from one or more repeating unitsconnected by covalent chemical bonds.

The term “polymerization” refers to methods for chemically reactingrepeating units to form polymer chains. The type of polymerizationmethod may be selected from a wide variety of methods. Such methodsinclude, but are not limited to, free radical polymerization, such asclassical radical polymerization and controlled radical polymerization,Nitroxide Mediation Polymerization (NMP), Atom Transfer RadicalPolymerization (ATRP), and Reversible Addition FragmentationChain-Transfer (RAFT). The term polymerization” also refers tocondensation polymerization methods.

The term “homopolymer” refers to a polymer comprising essentially onetype of repeating unit. Homopolymers include polymers polymerized fromone repeating unit that may be modified during or after polymerization,for example, by grafting, hydrolyzing, or end-capping. Homopolymers maybe associated with solvent adducts.

The term “non-homopolymer” refers to a polymer obtained bypolymerization of two or more different kinds of repeating units. Thedefinition includes essentially all polymers that are not homopolymers.Nonlimiting examples of non-homopolymers include copolymers,terpolymers, tetramers, and the like, wherein the non-homopolymer may bea random, block, or an alternating polymer.

The term “hydrophilic” refers to a molecular entity that tends to bepolar and water-soluble or water-miscible. A hydrophilic molecule orportion of a molecule may be charge-polarized and/or capable of hydrogenbonding enabling it to dissolve in water.

The term “hydrophobic” refers to a molecular entity that tends to benon-polar and non-water-soluble.

The term “inert solvent” refers to a solvent that does not interferechemically with the reaction.

The term “lower molecular weight alcohols” refers to alcohols havingfrom one to four carbon atoms. Examples of lower molecular weightalcohols include: methanol, ethanol, 1-propanol, 2-propanol, allylalcohol, propargyl alcohol, 2-aminoethanol, ethylene glycol, methylpropargyl alcohol, 1-butyn-4-ol, 2-butyn-1-ol, 2-buten-1-ol, 2-butanol,2-methyl-2-propanol, and tert-butanol. In various embodiments of theinvention, the lower molecular weight alcohol may be methanol, ethanol,1-propanol, 2-propanol, or tert-butanol, or combinations thereof.

The term “quaternary ammonium cation” , also known as “quat,” refers toa positively charged polyatomic ion having the structure NR′₄ ⁺, whereineach of the four R′ independently can be an alkyl group or an arylgroup. Unlike the ammonium ion (NH₄ ⁺) and primary, secondary, andtertiary ammonium cations, the quaternary ammonium cations arepermanently charged, independent of the pH value of their solution.Accordingly, quaternary ammonium cations are accompanied by an anion(negative charge) to balance the overall charge.

The term “each independently selected from the group consisting of”means that when a group appears more than once in a structure, thatgroup may be independently selected each time it appears. For example,in the structure below:

the generic substituent R₆ appears more than once. The term “eachindependently selected from the group consisting of” means that eachgeneric substituent may be the same or different.

The term “weight-average molecular weight” refers to a method ofdescribing the molecular weight of a polymer, and may be calculated bythe equation:

$M_{w} = \frac{\sum_{i}{N_{i}M_{i}^{2}}}{\sum_{i}{N_{i}M_{i}}}$

wherein N_(i) is the number of molecules having molecular weight M_(i).

The term “number-average molecular weight” refers to another method ofdescribing the molecular weight of a polymer, and may be calculated bythe equation:

$M_{n} = \frac{\sum_{i}{N_{i}M_{i}}}{\sum_{i}N_{i}}$

wherein N_(i) is the number of molecules having molecular weight M_(i).

The term “personal care composition,” also referred to as “cosmetics,”refer to such illustrative non-limiting compositions as skin, sun, oil,hair, and preservative compositions, including those to alter the color,condition, or appearance of the skin. Potential personal carecompositions include, but are not limited to, compositions for increasedflexibility in styling, durable styling, increased humidity resistancefor hair, skin, color cosmetics, water-proof/resistance,wear-resistance, and thermal protecting/enhancing compositions. Examplesof personal care compositions include: skin lotion, skin creme, skinointment, skin salve, anti-aging creme, moisturizer, deodorant, tanningagent, sun block, sunscreen, foundation, concealer, eyebrow pencil, eyeshadow, eye liner, mascara, rouge, finishing powder, lipstick, lipgloss, nail polish, make-up remover, nail polish remover, shampoo,rinse-off conditioner, leave-on conditioner, hair styling gel, hairmousse, hair spray, styling aide, hair color, or hair color remover.

The term “performance chemicals composition” refers to any non-personalcare composition. Performance chemicals compositions serve a broadspectrum of arts, and include non-limiting compositions such as:adhesives; agricultural, biocides, coatings, electronics,household-industrial-institutional (HI&I), inks, membranes, metalfluids, oilfield, paper, paints, plastics, printing, plasters, andwood-care compositions.

The term “oilfield formulation” refers to a composition that may be usedin the exploration, extraction, recovery, or completion of anyhydrocarbon-based fuel. Non-limiting examples of oilfield formulationsinclude anti-agglomerants, emulsifiers, de-emulsifiers, gas hydrateinhibitors, kinetic hydrate inhibitors, shale swelling inhibitors,drilling fluids, drilling muds, friction reducers, rheology modifier,fracturing fluids, and/or scale inhibitors.

The term “coating formulation” refers to any composition suitable forapplication on a substrate in order to provide one or more desiredfunctions, including, but not limited to protecting, smoothing,strengthening, decorating, color enhancing/altering, substrate preparingand/or texturizing. The substrate for a coating formulation may include,without limitation, paper, paper board, wood, inorganic substrate, wovenand non-woven textiles, metal, leather, powder, plastic, polymer, glass,cement, ceramic, traffic, tile, rubber, sealant, cable, concrete,plasterboard, adhesives, fillers, primers, inks, fertilizers,pharmaceuticals, structural materials, molding, printing, inks, and thelike. Examples of coating formulations include, without limitation, thefollowing: paints, primers, stains, sealers, varnishes/polyurethanes,adhesives, waterproofers, wood hardeners. Coating formulations may beapplied by brush, dauber, roll, strip/sheet, and/or trowel, or may beatomized and applied as a spray, mist, or droplet.

A “paint formulation” is a non-limiting, specific type of a “coatingformulation”. Paints may be water based or non-water based (i.e.,solvent based). Paint formulations may be designed for any number ofsubstrates, including wood, siding, dry wall, plaster, plastics,masonry, brick, tile, particle board, glass, stucco, concrete, and thelike. Non-limiting examples of paints include exterior paints, interiorpaints, architectural paints, and automotive paints.

The term “imide” refers to an organic compound comprising two carbonylgroups (acyl groups) bound to a common nitrogen atom. The nitrogen atomin the imide functional group may or may not be substituted with anorganic functional group.

The term “Jeffamine” is a brand name of The Huntsman Corporate andrefers to polyetheramines containing primary amino groups attached tothe end of a polyether backbone. The polyether may be based on eitherpropylene oxide (PO), ethylene oxide (EO), or mixed PO/EO. Thepolyetheramines undergo typical amine reactions, often impartingincreased flexibility, toughness, low viscosity, and low color. The widerange of molecular weight, amine functionality, repeating unit type, anddistribution can provide flexibility in the design of new compounds ormixtures. Jeffamines are available from Huntsman Corporation, TheWoodlands, Tex.

Multifunctional polymers have been discovered that are polymerized fromat least repeating unit (or repeat unit) types: A first repeating unit Acomprising at least one pseudo-cationic moiety, a second repeating unitB that comprises at least one hydrophobic moiety, and a third repeatingunit C, and wherein the weight-average molecular weight of the polymeris less than about 10,000 Da. Without being bound by theory, it isbelieved that the combination of repeating units A and B contributeantimicrobial activity, and repeating unit C allows for additionalperformance functionality.

The polymers may be random, block, or alternating, or combinationsthereof.

At least two broad categories of polymers are embraced by the invention,their repeating unit (or repeat unit) types determined in part by thepolymerization method. Multifunctional polymers prepared by a radicalpolymerization approach are summarized first, followed by polymerssynthesized by condensation polymerization. These polymers comprise atleast one first repeating unit A, at least one second repeating unit B,and at least one third repeating unit C.

By a radical polymerization method, repeating unit A may be anyrepeating unit having at least one pseudo-cationic moiety. For example,repeating unit A may be an amino (meth)acrylate, amino (meth)acrylamide,or a repeating unit comprising a nitrogen or phosphorus heterocyclicring, or combinations of these repeating units. These repeating unitsmay exhibit pseudo-cationic behavior, e.g., in acid conditions, e.g., byprotonation under acidic conditions.

In the embodiments wherein repeating unit A is an amino (meth)acrylateor an amino (meth)acrylamide , it may be represented by the structure:

-   wherein-   R₁, is selected from the group consisting of hydrogen, methyl, and    combinations thereof;-   R₂ and R₃ are independently selected from the group consisting of    C1-C20 alkyl,-   Q is selected from the group consisting of functionalized and    unfunctionalized alkylene, cycloalkylene, alkyleneoxy, alkenylene,    and arylene; and-   X is O or NH or combinations thereof.

In the amino (meth)acrylate and amino (meth)acrylamide structurepresented earlier, R₁ may be hydrogen or methyl, such that repeatingunit A may be regarded as an amino (meth)acrylate or amino(meth)acrylamide:

where R₂, R₃, and Q retain their earlier definitions. Particularly, Qmay be C1-C8 alkylene, more particularly C2-C5 alkylene. R₂ and R₃ maybe C1-C4 alkyl groups. Non-limiting examples of the second repeatingunit include:

Optionally, repeating unit A may comprise a nitrogen or phosphorusheterocyclic ring, such as functionalized and unfunctionalized N-vinyllactams, vinyl pyridines, vinyl imidazoles, and/or vinyl pyrazoles.Included in this aspect of the invention are the following polymerizablecompounds: N-vinyl imidazole, N-vinyl benzimidazole, N-vinyl-pyrazole,N-vinyl-3-imidazoline, N-(C1-C20-alkyl)-N′-vinyl piperazine or 2-, 3- or4-vinyl pyridine, and hydroxyethylimidazole (meth)acrylate. One or moreC1-C20-alkyl groups, which can be substituents in the aforementionedrepeating units can be methyl, ethyl, n-propyl, iso-propyl, n-butyl,iso-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl,n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl,2-propylheptyl, n-decyl, n-dodecyl, n-tridecyl, iso-tri-decyl,n-tetradecyl, n-hexydecyl, n-octadecyl and eicosyl.

Combinations of the repeating units may be used.

Turning now to repeating unit B, it is repeating unit comprising atleast one hydrophobic moiety. Thus, repeating unit B may be anypolymerizable repeating unit that exhibits hydrophobic character, oranother polymer having been functionalized with one or more hydrophobicmoieties. Within the context of radical polymerization, repeating unit Bmay be any functionalized and unfunctionalized: (meth)acrylates,(meth)acrylamides, styrenes, 4-vinyl-1,2,3-triazoles,5-vinyl-1,2,3-triazoles, vinyls, allyls, maleic anhydrides, fumarates,maleates, maleimides, α-β-olefinically unsaturated carboxylic nitriles,styrenes, vinyl ethers, vinyl esters, vinyl acetates, vinyl amides,vinyl alcohols, vinyl carbonates, vinyl carbamates, vinylthiocarbamates, vinyl ureas, vinyl halides, vinyl imidazoles, vinyllactams, vinyl pyridines, vinyl silanes, vinyl siloxanes, vinylsulfones, and/or allyl ethers.

Examples of hydrophobic alpha-olefins include isobutene, diisobutene,butene, pentene, hexene and additional olefins having 5 or more carbonatoms or mixtures thereof, such as, for example, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene,1-tetracosene and 1-hexacosene. The hydrophobic alpha-olefin may be aC₂₂-alpha-olefin, a mixture of C₂₀-C₂₄-alpha-olefins and polyisobutenewith, on average, 12 to 100 carbon atoms.

Further examples of hydrophobic repeating units B are known, includingthe (meth)acrylate and (meth)acrylamide families of repeating units.Includes in these classes are those repeating units represented by thestructure:

-   wherein-   R₄ is selected from the group consisting of hydrogen, methyl, and    combinations thereof,-   R₅ is selected from the group consisting of functionalized and    unfunctionalized alkyl, alkoxy, cycloalkyl, alkenyl, and aryl, and-   X is selected from the group consisting of O, NH, and combinations    thereof.

Non-limiting examples of hydrophobic (meth)acrylates include: ethylmethacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexylmethacrylate, methyl methacrylate, lauryl methacrylate, isobutylmethacrylate, isodecyl methacrylate, phenyl methacrylate, decylmethacrylate, 3,3,5-trimethylcyclohexyl methacrylate, benzylmethacrylate, cyclohexyl methacrylate, stearyl methacrylate, tert-butylmethacrylate, tridecyl methacrylate, 2-naphthyl methacrylate,2,2,3,3-tetrafluoropropyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropylmethacrylate, 2,2,2-trifluoroethyl methacrylate,2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,4,4,4-hexafluorobutylmethacrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate,2,2,3,3,4,4,5,5-octafluoropentyl methacrylate,3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate, and3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate.

Hydrophobic repeating units B also are provided when X is NH. As withthe (meth)acrylates, in particular embodiments R₅ may comprise 2 or morecarbon atoms, and more particularly, from about 4 to about 50 or evenmore carbon atoms, and yet more particularly from about 4 to 30 carbonatoms. Non-limiting examples of hydrophobic (meth)acrylamides include:ethyl (meth)acrylamide, butyl (meth)acrylamide, hexyl (meth)acrylamide,2-ethylhexyl (meth)acrylamide, octyl (meth)acrylamide, lauryl(meth)acrylamide, isobutyl (meth)acryl amide, isodecyl (mcth)acrylamidc,phenyl (meth)acrylamide, decyl (mcth)acrylamidc,3,3,5-tri(methyl)cyclohexyl (meth) acrylamide, benzyl (meth)acrylamide,cyclohexyl (meth)acrylamide, stearyl (meth)acrylamide, tert-butyl (meth)acrylamide, tridecyl (meth)acrylamide, 2-naphthyl (meth)acrylamide,2,2,3,3-tetrafluoropropyl (meth)acrylamide,1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylamide, 2,2,2-trifluoroethyl(meth)acrylamide, 2,2,3,3,3-pentafluoropropyl (meth)acrylamide,2,2,3,4,4,4-hexafluorobutyl (meth)acrylamide,2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylamide,2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylamide,3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth)acrylamide, and3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(meth)acrylamide.

The invention embraces other hydrophobic repeating units, such as thestyrene family of repeating units. Non-limiting examples thereof includethe following: 1-vinyl naphthalene, 2-vinyl naphthalene, a-methylstyrene, 3-methyl styrene, 4-propyl styrene, t-butyl styrene,4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, and4-(phenyl butyl) styrene.

Examples of hydrophobic alkyl vinyl ethers that may be used as repeatingunit B include methyl vinyl ether, ethyl vinyl ether, iso-propyl vinylether, n-butyl vinyl ether, iso-butyl vinyl ether, sec-butyl vinylether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether,hexadecyl vinyl ether, octadecyl vinyl ether, and combinations thereof.

It was mentioned earlier that the hydrophobic repeating unit B may be arepeating unit that is functionalized to impart hydrophobic character.Such functionalization includes those reactions to graft, add, orsubstitute one or more hydrophobic moieties to the repeating unit orpolymer. To help illustrate this point, a suitable hydrophobic repeatingunit B may be attained by reacting a polymerizable anhydride with acompound having at least one moiety that is reactive to the anhydride.The anhydride may be maleic anhydride, methyl maleic anhydride, dimethylmaleic anhydride, itaconic anhydride, citraconic anhydride, andtetrahydrophthalic anhydride, as well as their functionalized analogues.The moiety reactive to the anhydride may be a hydroxyl, amine, or thiolmoiety so that a hydrophobically-modified anhydride results. Thehydrophobic moiety may be any functionalized or unfunctionalizedalkylene, alkyleneoxy, cycloalkylene, alkenylene, arylene with orwithout heteroatoms, and combinations thereof. Particularly, thehydrophobic moiety may comprise 2 to 50 carbon atoms, more particularlyfrom 2 to 20 carbon atoms. The modification may be realized through thehydrophobic modification of the pre-polymerized repeating unit, or afterpolymerization with intact reactive groups on the polymer.

Polymers of the invention are polymerized from at least a repeating unitC that is chosen in order to modulate the polymer's properties asappropriate. Monomer C may be hydrophobic, hydrophilic, or amphiphilic;combinations may be used. One or more repeating unit C may be selectedfrom the group consisting of functionalized and unfunctionalized:(meth)acrylates, (meth)acrylamides, styrenes, 4-vinyl-1,2,3-triazoles,5-vinyl-1,2,3-triazoles, vinyls, allyls, maleic anhydrides, fumarates,maleates, maleimides, α-β-olefinically unsaturated carboxylic nitriles,styrenes, vinyl ethers, vinyl esters, vinyl acetates, vinyl amides,vinyl alcohols, vinyl carbonates, vinyl carbamates, vinylthiocarbamates, vinyl ureas, vinyl halides, vinyl imidazoles, vinyllactams, vinyl pyridines, vinyl silanes, vinyl siloxanes, vinylsulfones, allyl ethers, and combinations thereof. One skilled in the artunderstands how to polymerize these repeating units with repeating unitsA and B, e.g., radical, emulsion, cationic, anionic polymerizationmethods.

In one non-limiting example, repeating unit C is an amide, and may be anN-vinyl amide represented by the structure:

wherein R₆ and R₇ are selected from the group consisting offunctionalized and unfunctionalized alkyl, alkoxy, cycloalkyl, alkenyl,and aryl groups, and where R₆ and R₇ may form a ring having from 5 to 7carbon atoms.

In one embodiment, R₆ and R₇ may be independently selected from thegroup consisting of hydrogen and methyl. Examples of repeating unit C inthis embodiment may include repeating units represented by thestructure:

and combinations thereof.

Alternatively, R₆ and R₇ may form a ring structure, and repeating unit Cmay be represented by the structure:

where n is an integer from 1 to 3. Examples of such repeating unitsinclude those having the structures:

and combinations thereof.

In another embodiment, repeating unit C may be a (meth)acrylate and/or(meth)acrylamide, such as those described earlier for repeating unit Bexcept repeating unit C does not have to be hydrophobic.

Other examples of repeating unit C include, without limitation:

wherein each R is independently selected from the group consisting ofhydrogen, and functionalizcd and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the beforementioned groups maybe with or without heteroatoms, and m and n are integers greater than orequal to 1.

Combinations of repeating units A, B, and/or C may be used (i.e., themultifunctional polymer may be a terpolymer, a tetrapolymer, or comprisemore than 4 repeat units).

In addition to radical polymerization, polymers embraced by theinvention include those synthesized by condensation polymerization.Maintained in this aspect of the invention are the descriptions ofrepeating units A (comprises a pseudo-cationic moiety), B (comprises ahydrophobic moiety), and repeating unit C. Polymers having aweight-average molecular weight of less than about 10,000 Da can be madeby either radical or condensation polymerization methods; the slowerreaction rate for condensation may allow better control of the finalpolymer properties.

Next, a brief description is provided for the repeating units when themultifunctional polymer is a condensation polymer.

Monomer A may be any multifunctional compound comprising at least onepseudo-cationic moiety and at least two reactive groups suitable forcondensation polymerization. Examples of these reactive groups include,but are not limited to, hydroxyl and thiol groups. The pseudo-cationicmoiety may comprise a nitrogen atom, such as amino or comprise anitrogen or phosphorus heterocyclic ring. Examples of nitrogenheterocyclic rings include lactamyl, pyridinyl, imidazolyl, andpyrazolyl moieties. Typical condensation repeating units A may have thestructure:

X-Q₂-X

-   wherein-   Q₂ is selected from the group consisting of functionalized and    unfunctionalized alkylene, cycloalkylene, alkyleneoxy, alkenylene,    and arylene, wherein Q₂ comprises one or more pseudo-cationic    moieties pendant to or part of the final polymer backbone;-   each X is independently selected from the group consisting of O and    SH; and

Examples of condensation repeating units A include, but arc not limitedto:

and combinations thereof.

Condensation repeating units B are those repeating units comprising atleast one hydrophobic moiety, which may be pendant to or part of thefinal polymer backbone. In one embodiment, condensation repeating unit Bis a polymerizable condensation repeating unit also having at least tworeactive groups suitable for condensation polymerization. Thehydrophobic group may or may not be pendant to the final polymerbackbone. Such condensation repeating units B may have the structure:

X-Q₃-X

-   wherein-   Q₃ is selected from the group consisting of functionalized and    unfunctionalized alkylene, cycloalkylene, alkyleneoxy, alkenylene,    and arylene, wherein Q₃ comprises one or more hydrophobic moieties    pendant to or part of the final polymer backbone;-   each X is independently selected from the group consisting of O and    SH; and

Examples of condensation repeating units B include, but are not limitedto:

and combinations thereof.

Alternatively, the condensation repeating unit B is not a polymerizablecondensation repeating unit per se, yet still repeats more than onethroughout the polymer. The hydrophobic moiety may be provided byend-capping or grafting one or more hydrophobic moieties onto acondensation polymer. Such reactions are known to one skilled in theart, and may be accomplished, e.g., by reacting a polymer bearingreactive hydroxyl or amino groups with a compound having the structure:

R*-W

-   wherein-   R* is a hydrophobic moiety selected from the group consisting of    alkyl, alkoxyl, cycloalkyl, alkenyl, and aryl, wherein any of the    beforementioned groups may be with or without one or more    heteroatoms, and-   W is halogen,-   under alkaline conditions (for example, with NaOH addition).

Multifunctional polymers that are condensation polymers also compriserepeating unit C, which can be any functional repeating unit having thestructure:

X-Q₄-X

-   wherein-   Q₄ is selected from the group consisting of functionalized and    unfunctionalized alkylene, cycloalkylene, alkyleneoxy, alkenylene,    and arylene;-   each X is independently selected from the group consisting of O and    SH; and

Non-limiting examples of condensation repeating units C include thefollowing compounds:

and combinations thereof.

Also suitable are polyetheramines, such as those based on propyleneoxide and/or ethylene oxide, such as those sold into commercial saleunder the trade name “Jeffamine” by The Huntsman Corporation.

Condensation multifunctional polymers may be prepared by reactingrepeating units A, B, and C in the presence of one or more hydrocarbylcompounds having at least two halogens:

W-Q*W

-   wherein-   Q* is functionalized and unfunctionalized hydrocarbylene optionally    having one or more heteroatoms, and-   each W is independently selected halogen.

A non-limiting reaction scheme illustrating condensation multifunctionalpolymers is given by:

wherein A, B, C, and k represent the molar quantities of each reactanttype. The silicone-containing compound is disclosed in Journal of theAmerican Chemical Society, 1959 , vol. 81, p. 2632.

As mentioned earlier, the reactive hydroxyl and amine groups may besubject to one or more further reactions, e.g., to produce an end-cappedor grafted condensation polymer.

Additionally, multifunctional polymers comprising repeating units A, B,and C may be prepared by ring-opening polymerization of functionalizedand unfunctionalized cyclic compounds. For example, monomer A may be afunctionalized ethylene oxide having a pseudo-cationic moiety, such as:

monomer B may be a functionalized ethylene oxide having at least onehydrophobic moiety, such as:

and monomer C may be any functionalized or unfunctionalized ethyleneoxide, such as:

Other functionalized and unfunctionalized cyclic compounds with andwithout heteroatoms, including oxetanes, tetrahydrofurans, oxazines, andoxazolines, may be polymerized to yield corresponding multifunctionalpolymers according to the invention.

In one embodiment, the multifunctional polymer comprising repeatingunits A, B, and C may be a terpolymer, whether it be a radicalpolymerization polymer or a condensation polymer. It may be representedas:

-   wherein:-   said M_(pseudo-cationic) is a repeating unit comprising at least one    pseudo-cationic moiety,-   said M_(hydrophobic) is a repeating unit comprising at least one    hydrophobic moiety,-   said M_(funcational) is a functional repeating unit,-   and wherein said a, b, and c are molar ratios totaling 100%.

The reader will recognize that M_(pseudo-cationic) is repeating unit A,M_(hydrophobic) is repeating unit B, and M_(functional) is repeatingunit C as described earlier. For brevity, non-limiting descriptions forthese repeating units will be understood to apply for terpolymerembodiments.

An aspect of this embodiment is a multifunctional radical polymerizationpolymer represented by the structure:

-   wherein:-   R₁, R₄, and R₅ are independently selected from the group consisting    of functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl,    alkenyl, and aryl groups;-   R₂ and R₃ are C₁-C₅ alkyl groups,-   R₆ and R₇ are independently selected from the group consisting of    functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl,    alkenyl, and aryl groups, and R₆ and R₇ may form a 5 to 7-membered    ring,

X is O or NH or combinations thereof,

-   Q is selected from the group consisting of functionalized and    unfunctionalized alkylene, alkyleneoxy, cycloalkylene, alkenylene,    and arylene groups, and-   and the subscripts a, b, and c refer to the molar amounts of the    three repeating units.

The invention embraces various embodiments with regard to genericsubstituent. For example, in various aspects Q may be C₁-C₅ alkylene,more particularly C₁-C₄ alkylene; or yet more particularly propylene.Various aspects of R₅ include C₃-C₁₈ alkyl, more particularly C₄-C₁₆alkyl, and yet more particularly C₄-C₁₂ alkyl. R₁ and R₄ may be hydrogenor methyl; more particularly, they are methyl. In one aspect, R₂ and R₃may be C₁-C₃ alkyl; more particularly C₁-C₂ alkyl; and yet moreparticularly methyl. Regarding the molar subscripts, a may range fromabout 5% to about 80%, b may range from about 5% to about 60%, and c mayrange from about 5% to about 80%. More particularly, a may range fromabout 10% to about 70%, b may range from about 15% to about 50%, and cmay range from about 10% to about 70%. In one aspect, the weight-averagemolecular weight of the polymer may be less than 10,000 Da.

In one of the terpolymer embodiments, the invention providesamphiphilic, pseudo-cationic multifunctional polymers. Themultifunctional polymers may be prepared by a polymerization of: (A) apseudo-cationic vinyl repeating unit such as N[2-(dimethylamino)ethyl](meth)acrylamide, N-[3-(dimethylamino)propyl] (meth)acrylamide, orN-[4-(dimethylamino)butyl] (meth)acrylamide; with (B) a hydrophobicvinyl repeating units; such as methyl (meth)acrylate, ethyl(meth)acrylate, or butyl (meth)acrylate, and (C) N-vinyl amide repeatingunit; such as N-vinyl formamide, N-methyl-N-vinyl formamide, N-vinylpyrrolidone, and/or N-vinyl caprolactam. In one aspect, the polymer maybe represented by the structures:

wherein a, b, and c are as defined above.

Also embraced by the invention is a method of providing antimicrobialactivity in or on a composition, wherein the method comprising the step:contacting a composition with at least one multifunctional polymersynthesized from at least repeating unit types: a first repeating unit Acomprising at least one pseudo-cationic tertiary amine, a secondrepeating unit B that is hydrophobic, and a third repeating unit C.Separately, the weight-average molecular weight of the polymer may beless than about 10,000 Da. The molecular weight may be chosen, in part,based on the addition level of the multifunctional polymer,multifunctional polymer type, rheology considerations, and desired levelof antimicrobial activity. Descriptions of the method's repeating unitsA, B, and C mirror the description provided earlier, and for the sake ofbrevity are not repeated here.

In one embodiment, the method's polymer may be a terpolymer, and may berepresented as:

-   wherein:-   said M_(pseudo-cationic) is a repeating unit comprising at least one    pseudo-cationic moiety,-   said M_(hydrophobic) is a repeating unit comprising at least one    hydrophobic moiety,-   said M_(functional) is a functional repeating unit,-   and wherein said a, b, and c are molar ratios totaling 100%.

Particularly but without limitation, the polymer may be represented bythe structure:

-   wherein:-   R₁, R₄, and R₅ are independently selected from the group consisting    of functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl,    alkenyl, and aryl groups;-   R₂ and R₃ are C₁-C₅ alkyl groups,-   R₆ and R₇ arc independently selected from the group consisting of    functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl,    alkenyl, and aryl groups, and R₆ and R₇ may form a 5 to 7-membered    ring,-   X is O or NH or combinations thereof,

Q is selected from the group consisting of functionalized andunfunctionalized alkylene, alkyleneoxy, cycloalkylene, alkenylene, andarylene groups, and

-   and the subscripts a, b, and c refer to the molar amounts of the    three repeating units.

Non-limiting examples of polymers that may be used in the methodinclude:

wherein a, b, and c arc as defined above.

The aforementioned method comprises the step, “contacting a compositionwith a multifunctional polymer” meaning that the composition may bemolecular blend, a nano/micro/macroscopic dispersion, and/ornano/micro/macroscopic emulsion with one or more multifunctionalpolymer(s). Additionally, the composition may contact one or moremultifunctional polymer(s) at an interface, e.g., as a film, in one ormore layers, and/or along a phase boundary.

In one embodiment, the method provides antimicrobial activity against amicrobe selected from the group consisting of S. aureus, E. coli, P.aeruginosa, A. niger, C. albicans, and combinations thereof. In aseparate embodiment, the multifunctional polymers express antimicrobialactivity at a microorganism concentration of 10⁵-10⁶ cfu/mL and apolymer concentration of 1% (w/w) or greater.

The polymers may be designed to have a wide variety of physical andmechanical properties, to suit a particular application. The polymersmay be random, block, or alternating polymers, or combinations thereof.The properties of the multifunctional polymers can be further designedby appropriate selection of the type of the vinyl repeating unitsemployed, the ratios of the vinyl repeating units employed, and theweight-average molecular weight of the resulting polymer.

In another aspect, a wide variety of compositions comprising themodified polymers are provided, including adhesives, aerosols,agricultural compositions, beverages, biocides, cleaning compositions,coating compositions, cosmetic compositions, dental compositions,detergents, drugs, electronics, encapsulations, foods, hair sprays,household-industrial-institutional (HI&I), inks, lithographic solutions,membrane compositions, metal fluids, oilfield compositions, paints,paper, personal care compositions, pharmaceuticals, plasters, plastics,printing, and wood-care compositions.

Polymers of the invention may be used in a wide variety of compositionssuch as in adhesives, agricultural, biocides, coatings, electronics,household-industrial-institutional inks, membranes, metal fluids,oilfield, paper, paints, plastics, printing, plasters, and wood-carecompositions.

Depending on the end application, one or more fillers may be included inthe compositions and may be added for improved rheological propertiesand/or stress reduction. Examples of suitable nonconductive fillersinclude alumina, aluminum hydroxide, silica, fused silica, fumed silica,vermiculite, mica, wollastonite, calcium carbonate, titania, sand,glass, barium sulfate, zirconium, carbon black, organic fillers, andhalogenated ethylene polymers, such as, tetrafluoroethylene,trifluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidenechloride, and vinyl chloride. Examples of suitable conductive fillersinclude carbon black, graphite, gold, silver, copper, platinum,palladium, nickel, aluminum, silicon carbide, boron nitride, diamond,and alumina. Combinations of these fillers may be used.

The filler particles may be of any appropriate size, particularly fromthe nano to micro range. The choice of such size for any particular enduse is within the expertise of one skilled in the art. The filler may bepresent in an amount from about 10% to about 90% by weight of the totalcomposition. More than one filler type may be used in a composition andthe fillers may or may not be surface treated. Appropriate filler sizescan be determined by the practitioner, and, in particular, may be withinthe range from about 20 nm to about 100 min.

Other materials, such as adhesion promoters (e.g. epoxides, silanes),dyes, pigments, and rheology modifiers may be added as desired for themodification of the final properties. Such materials and the amountsneeded are within the expertise of those skilled in the art.

Compositions belonging to the personal care/cosmetic and pharmaceuticalarts find utility in altering, delivering an active, enhancing,improving, modifying the appearance, condition, color, health, style ofthe skin (including face, scalp, and lips), hair, nails, and oralcavity. Many examples and product forms of these compositions are known.These compositions can impart benefits that include, but are not limitedto, hair style flexibility, hair style durability, humidity resistancefor hair, color and/or color protection, moisturization, wrinklereduction, protection from ultraviolet radiation, water proofness, waterresistance, wear resistance, thermal protection, adhesion, activeingredient delivery, anti-cavity, and/or anti-gingivitis protection. Assuch, these compositions are sometimes categorized in the followingareas: skin care, hair care (both styling and non-styling), sun care,cosmetics (including color cosmetics), antiperspirants, deodorants, oralhygiene, and men's and women's personal hygiene/grooming. In some casesthese benefits and care areas overlap with another.

Skin care compositions include those materials used on the body, face,hands, lips, and/or scalp, and are beneficial for many reasons, such asfinning, anti-cellulite, moisturizing, nourishing, cleaning, reducing oreliminating the appearance of wrinkles or lentigo, toning, and/orpurifying. They also can be used to sanitize.

Consumers can identify many of the compositions that serve the sun carearea, for example after-fun, children's, beach, self-tan, sports (i.e.,being sweat proof, waterproof, resistant to running, or having added UVabsorbers and/or antioxidants), sensitive skin products (i.e., havinglow irritation to the eyes and/or skin, and/or being free of fragrancesand/or dyes), daily wear, leave-on hair creams, lotions, stylingproducts, and hair sprays. Typically, sun care products also compriseone or more UV actives, which are those organic and inorganic materialsthat scatter, absorb, and/or reflect radiation having a wavelength fromabout 100 nm to about 400 nm. In one aspect, the sun care productprotects against UV-A and/or UV-B radiation. UV-A radiation, from about320 nm to about 400 nm, has the longest wavelength within the UVspectrum, and consequently is the least energetic. While UV-A rays caninduce skin tanning, they are liable to induce adverse changes as well,especially in the case of sensitive skin or of skin, which iscontinually exposed to solar radiation. In particular UV-A rays cause aloss of skin elasticity and the appearance of wrinkles, leading topremature skin aging. UV-B rays have shorter wavelengths, from about 290nm to about 320 nm, and their higher energy can cause erythema and skinburns, which may be harmful. Alternatively, sun care products may omitUV actives, and may be regarded as a tanning oil or a tan promoter. Somesun care compositions may promote soothe skin after sun exposure, and/orbe formulated for application to the lips, hair, or the area around theeyes. Self-tan compositions, which are products that color skin withoutrequiring full sun exposure, also fit under the sun care umbrella. Themany different sun care product formats include may assume a consistencyranging from liquid to semi liquid forms (e.g., milks, creams), tothicker forms like gels, creams, pastes, and even solid- and wax-likeforms. Sun care products also may take the form of an aerosol, spray,mist, roll-on, or wipe.

Hair care compositions include shampoos, leave-on and rinse-outconditioners used for conditioning, moisturizing, repairing, haircolors, hair relaxers, and deep conditioners and treatments such as hotoils and waxes, 2-in-1 shampoo/conditioner combination products, 3-in-1shampoo/conditioner/styling agent. The many types of hair care productscan be delivered in an array of formats, including aerosol sprays, pumpsprays, gel sprays, mousses, gels, waxes, creams, pomades, spritzes,putties, lacquers, de-frizzing serums, perms, relaxants and colorants.

Color cosmetic compositions include facial make-up, eye makeup,mascaras, lip and nail products. Facial make-up compositions includefoundation (liquid, solid, and semi-solid)—skin tinted creams, liquid,sticks, mousses used as a base under make-up, rouge, face powder,blusher, highlighters, face bronzers, concealers, and 2-way cakeproducts.

Personal care/cosmetics also include eye make-up, mascaras, eyeliners,eye shadows, eyebrow pencils and eye pencils. Lip products includelipsticks, lip pencils, lip gloss, transparent bases and tinted lipmoisturizers as well as multi-function color sticks that also can beused for cheeks and eyes. Nail products include nail varnishes/enamels,nail varnish removers, treatments, home-manicure products such ascuticle softeners and nail strengtheners.

In addition to the skin, hair, and sun care compositions summarizedabove, the polymers related herein also find application in oral carecompositions. Non-limiting examples or oral care compositions includetoothpastes (including toothpaste gels), denture adhesives, whiteners,anesthetics, and dental floss and related products. These compositionsmay take any product format, such as pastes, gels, creams, solutions,dispersions, rinses, flosses, aerosols, powders, and lozenges.

Grooming products for men and women include shaving products andtoiletries, which may find use in preparing the skin and/or hair for dryor wet shaving. In addition, these compositions may help to moisturize,cool, and/or soothe skin. A variety of product forms are known, a few ofwhich are foams, gels, creams, sticks, oils, solutions, tonics, balms,aerosols, mists, sprays, and wipes.

The polymer also can be used in other personal care/cosmeticapplications, such as an absorbent material in appropriate applicationssuch as diapers, incontinence products, feminine products, and otherrelated products.

The polymers described herein also find application in bath and showercompositions, such as foams, gels, salts, oils, balls, liquids, powdersand pearls. Also included are bar soaps, body washes, shower gels,cleansers, gels, oils, foams, scrubs and creams. As a natural extensionof this category, these compositions also include liquid soaps and handsanitizers used for cleaning hands.

The polymer of the invention can be used in combination with one or moreadditional personal care/cosmetically acceptable additives chosen from,for example, conditioning agents, protecting agents, such as, forexample, hydrosoluble, liposoluble and water-insoluble UV filters,antiradical agents, antioxidants, vitamins and pro-vitamins, fixingagents, oxidizing agents, reducing agents, dyes, cleansing agents,anionic, cationic, nonionic and amphoteric surfactants, thickeners,perfumes, pearlizing agents, stabilizers, pH adjusters, filters, hydroxyacids, various cationic, anionic and nonionic polymers, cationic andnonionic polyether associative polyurethanes, preservatives, vegetableoils, mineral oils, synthetic oils, polyols such as glycols andglycerol, silicones, aliphatic alcohols, colorants, bleaching agents,highlighting agents and sequestrants.

These additives may be present in the composition according to theinvention in proportions that may range from about 0% to about 20% byweight in relation to the total weight of the composition. An expert inthe field according to its nature and its function may easily determinethe precise amount of each additive.

Examples of these co-ingredients and many others can be found in thefollowing references, each of which is herein incorporated in itsentirety by reference: “ Inventory and common nomenclature ofingredients employed in cosmetic products,” Official Journal of theEuropean Union, 5.4.2006, pages L 97/1 through L 97/528; andInternational Cosmetic Ingredient Dictionary and Handbook, 13th edition,ISBN: 1882621476, published by The Personal Care Products Council inJanuary 2010.

Any known conditioning agent is useful in the personal care/cosmeticcompositions of this invention. Conditioning agents function to improvethe cosmetic properties of the hair, particularly softness, thickening,untangling, feel, and static electricity and may be in liquid,semi-solid, or solid form such as oils, waxes, or gums. Similarly, anyknown skin-altering agent is useful in the compositions of thisinvention. A few examples of conditioning agents include cationicpolymers, cationic surfactants and cationic silicones. Conditioningagents may be chosen from synthesis oils, mineral oils, vegetable oils,fluorinated or perfluorinated oils, natural or synthetic waxes,silicones, cationic polymers, proteins and hydrolyzed proteins, ceramidetype compounds, cationic surfactants, fatty amines, fatty acids andtheir derivatives, as well as mixtures of these different compounds.

The cationic polymers that may be used as a conditioning agent accordingto the invention are those known to improve the cosmetic properties ofhair treated by detergent compositions. The expression “ cationicpolymer” as used herein, indicates any polymer containing cationicgroups and/or ionizable groups in cationic groups. The cationic polymersused generally have a number-average molecular weight, which fallsbetween about 500 and 5,000,000, for example between 1000 and 3,000,000.Cationic polymers may be chosen from among those containing unitsincluding primary, secondary, tertiary, and/or quaternary amine groupsthat may either form part of the main polymer chain or a side chain.Useful cationic polymers include known polyamine, polyaminoamide, andquaternary polyammonium types of polymers, such as:

-   -   a. homopolymers and copolymers derived from acrylic or        methacrylic esters or amides. The copolymers can contain one or        more units derived from acrylamides, methacrylamides, diacetone        acrylamides, acrylic or methacrylic acids or their esters, vinyl        lactams such as vinyl pyrrolidone or vinyl caprolactam, and        vinyl esters. Specific examples include: copolymers of        acrylamide and N,N-dimethylaminoethyl methacrylate quaternized        with dimethyl sulfate or with an alkyl halide; copolymers of        acrylamide and methacryloyloxyethyl trimethyl ammonium chloride;        the copolymer of acrylamide and methacryloyloxyethyl trimethyl        ammonium methosulfate; copolymers of vinyl        pyrrolidone/dialkylaminoalkyl acrylate or methacrylate,        optionally quaternized, such as the products sold under the name        Gafquat® by Ashland Specialty Ingredients; the        N,N-dimethylaminoethyl methacrylate/vinyl caprolactam/vinyl        pyrrolidone terpolymers, such as the product sold under the name        Gaffix® VC 713 by Ashland Specialty Ingredients; the vinyl        pyrrolidone/methacrylamidopropyl dimethyl amine copolymer,        marketed under the name Styleze® CC-10 by Ashland Specialty        Ingredients; the vinyl pyrrolidone/quaternized dimethyl amino        propyl methacrylamide copolymers such as the product sold under        the name Gafquat® HS-100 by Ashland Specialty Ingredients; and        the vinyl pyrrolidone/dimethylaminopropyl methacrylami de/C₉-C₂₄        alkyldimethylaminopropyl methacrylic acid quaternized        terpolymers described in U.S. Pat. No. 6,207,778 and marketed        under the name Styleze® W-20 by Ashland Specialty Ingredients.    -   b. derivatives of cellulose ethers containing quaternary        ammonium groups, such as hydroxyethyl cellulose quaternary        ammonium that has reacted with an epoxide substituted by a        trimethyl ammonium group.    -   c. derivatives of cationic cellulose such as cellulose        copolymers or derivatives of cellulose grafted with a        hydrosoluble quaternary ammonium repeating unit, as described in        U.S. Pat. No. 4,131,576, such as the hydroxy alkyl cellulose,        and the hydroxymethyl-, hydroxyethyl- or hydroxypropyl-cellulose        grafted with a salt of methacryloyl ethyl trimethyl ammonium,        methacrylamidopropyl trimethyl ammonium, or dimethyl diallyl        ammonium.    -   d. cationic polysaccharides such as described in U.S. Pat. Nos.        3,589,578 and 4,031,307, guar gums containing cationic trialkyl        ammonium groups and guar gums modified by a salt, e.g., chloride        of 2,3-epoxy propyl trimethyl ammonium.    -   e. polymers composed of piperazinyl units and alkylene or        hydroxy alkylene divalent radicals with straight or branched        chains, possibly interrupted by atoms of oxygen, sulfur,        nitrogen, or by aromatic or heterocyclic cycles, as well as the        products of the oxidation and/or quatemization of such polymers.    -   f. water-soluble polyamino amides prepared by polycondensation        of an acid compound with a polyamine. These polyamino amides may        be reticulated.    -   g. derivatives of polyamino amides resulting from the        condensation of polyalkylene polyamines with polycarboxylic        acids followed by alkylation by bi-functional agents.    -   h. polymers obtained by reaction of a polyalkylene polyamine        containing two primary amine groups and at least one secondary        amine group with a dioxycarboxylic acid chosen from among        diglycolic acid and saturated dicarboxylic aliphatic acids        having 3 to 8 atoms of carbon. Such polymers are described in        U.S. Pat. Nos. 3,227,615 and 2,961,347.    -   i. the cyclopolymers of alkyl diallylamine or dialkyl diallyl        ammonium such as the homopolymer of dimethyl diallyl ammonium        chloride and copolymers of diallyl dimethyl ammonium chloride        and acrylamide.    -   j. quaternary diammonium polymers such as hexadimethrine        chloride. Polymers of this type arc described particularly in        U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547,        3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432,        3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627,        4,025,653, 4,026,945, and 4,027,020.    -   k. quaternary polyammonium polymers, including, for example,        Mirapol® A 15, Mirapol® AD1, Mirapol® AZ1, and Mirapol® 175        products sold by Miranol.    -   l. the quaternary polymers of vinyl pyrrolidone and vinyl        imidazole such as the products sold under the names Luviquat® FC        905, FC 550, and FC 370 by BASF.    -   m. quaternary polyamines    -   n. reticulated polymers known in the art.

The conditioning agent can be a protein or hydrolyzed cationic ornon-cationic protein. Examples of these compounds include hydrolyzedcollagens having triethyl ammonium groups, hydrolyzed collagens havingtrimethyl ammonium and trimethyl stearyl ammonium chloride groups,hydrolyzed animal proteins having trimethyl benzyl ammonium groups(benzyltrimonium hydrolyzed animal protein), hydrolyzed proteins havinggroups of quaternary ammonium on the polypeptide chain, including atleast one C1-C18 alkyl. Hydrolyzed proteins include Croquat™ L, in whichthe quaternary ammonium groups include a C12 alkyl group, Croquat™ M, inwhich the quaternary ammonium groups include C10-C18 alkyl groups,Croquat™ S in which the quaternary ammonium groups include a C18 alkylgroup and Crotein Q in which the quaternary ammonium groups include atleast one C1-C18 alkyl group. These products are sold by Croda. Theconditioning agent can comprise quaternized vegetable proteins such aswheat, corn, or soy proteins such as cocodimonium hydrolyzed wheatprotein, laurdimonium hydrolyzed wheat protein and steardimoniumhydrolyzed wheat protein.

The conditioning agent can be a ceramide type of compound such as aceramide, a glycoceramide, a pseudoceramide, or a neoceramide. Thesecompounds can be natural or synthetic. Compounds of the ceramide typeare, for example, described in Patents pending DE4424530, DE4424533,DE4402929, DE4420736, WO95/23807, WO94/07844, EP-A-0646572, WO95/16665,FR-2 673 179, EP-A-0227994, WO 94/07844, WO 94/24097, and WO 94/10131.Ceramide type compounds useful herein include 2-N-linoleoylamino-octadecane-1,3-diol, 2-N-oleoyl amino-octadecane-1,3-diol,2-N-palmitoyl amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3-diol, 2-N-behenoyl amino-octadecane-1,3-diol,2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3,4-triol, N-stearoyl phytosphingosine, 2-N-palmitoylamino-hexadecane-1,3-diol, bis-(N-hydroxy ethyl N-cetyl) malonamide,N(2-hydroxy ethyl)-N-(3-cetoxyl-2-hydroxy propyl) amide of cetylic acid,N-docosanoyl N-methyl-D-glucamine and mixtures of such compounds.

The conditioning agent can be a cationic surfactant such as a salt of aprimary, secondary, or tertiary fatty amine, optionallypolyoxyalkylenated, a quaternary ammonium salt, a derivative ofimadazoline, or an amine oxide. Suitable examples include mono-, di-, ortri-alkyl quaternary ammonium compounds with a counter-ion such as achloride, methosulfate, tosylate, etc. including, but not limited to,cetrimonium chloride, dicetyldimonium chloride, behentrimoniummethosulfate, and the like. The presence of a quaternary ammoniumcompound in conjunction with the polymer described above reduces staticand enhances combing of hair in the dry state. The polymer also enhancesthe deposition of the quaternary ammonium compound onto the hairsubstrate thus enhancing the conditioning effect of hair.

The conditioning agent can be any fatty amine known to be useful as aconditioning agent; e.g. dodecyl, cetyl or stearyl amines, such asstearamidopropyl dimethylamine. The conditioning agent can be a fattyacid or derivatives thereof known to be useful as conditioning agents.Suitable fatty acids include myristic acid, palmitic acid, stearic acid,behenic acid, oleic acid, linoleic acid, and isostearic acid. Thederivatives of fatty acids include carboxylic esters including mono-,di-, tri- and tetra-carboxylic acids.

The conditioning agent can be a fluorinated or perfluorinated oil.Fluorinated oils include perfluoropolyethers described in EP-A-486135and the fluorohydrocarbon compounds described in WO 93/11103. Thefluoridated oils may also be fluorocarbons such as fluoramines, e.g.,perfluorotributylamine, fluoridated hydrocarbons, such asperfluorodecahydronaphthalene, fluoroesters, and fluoroethers. Ofcourse, mixtures of two or more conditioning agents can be used.

The conditioning agent can be any silicone known by those skilled in theart to be useful as a conditioning agent. The silicones suitable for useaccording to the invention include polyorganosiloxancs that arcinsoluble in the composition. The silicones may be present in the formof oils, waxes, polymers, or gums. They may be volatile or non-volatile.The silicones can be selected from polyalkyl siloxanes, polyarylsiloxanes, polyalkyl aryl siloxanes, silicone gums and polymers, andpolyorgano siloxanes modified by organofunctional groups, andcombinations thereof. Suitable polyalkyl siloxanes include polydimethylsiloxanes with terminal trimethyl silyl groups or terminal dimethylsilanol groups (dimethiconol) and polyalkyl (C1-C20) siloxanes. Suitablepolyalkyl aryl siloxanes include polydimethyl methyl phenyl siloxanesand polydimethyl diphenyl siloxanes, linear or branched. The siliconegums suitable for use herein include polydiorganosiloxanes includingthose having a number-average molecular weight between 200,000 and1,000,000, used alone or mixed with a solvent. Examples includepolymethyl siloxane, polydimethyl siloxane/methyl vinyl siloxane gums,polydimethyl siloxane/diphenyl siloxane, polydimethyl siloxane/phenylmethyl siloxane and polydimethyl siloxane/diphenyl siloxane/methyl vinylsiloxane. Suitable silicone polymers include silicones with adimethyl/trimethyl siloxane structure and polymers of the trimethylsiloxysilicate type. The organo-modified silicones suitable for use inthe invention include silicones such as those previously defined andcontaining one or more organofunctional groups attached by means of ahydrocarbon radical and grafted siliconated polymers. In one embodimentthe silicones are amino functional silicones. The silicones may be usedin the form of emulsions, nano-emulsions, or micro-emulsions.

The conditioning agent or agents can be present in an amount from about0.001% to about 20%, particularly from about 0.01% to about 10%, andeven more particularly from about 0.1% to about 3% by weight based onthe total weight of the final composition. The personal care/cosmeticcompositions of the invention can contain one or more protecting agentsin combination with the above-described polymer to prevent or limit thedegrading effects of natural physical and/or chemical assaults on thekeratinous materials.

The protecting agent can be chosen from hydrosoluble, liposoluble andwater-insoluble UV filters, antiradical agents, antioxidants, vitaminsand pro-vitamins. The above-described cationic polymer enhances thedeposition of these materials onto the hair or skin substrate enhancingprotection of hair to UV damage. Organic UV filters (systems that filterout UV rays) can be chosen from among hydrosoluble or liposolublefilters, whether siliconated or nonsiliconated, and mineral oxideparticles, the surface of which may be treated. Hydrosoluble organic UVfilters may be chosen from para-amino benzoic acid and its salts,anthranilic acid and its salts, salicylic acid and its salts, hydroxycinnamic acid and its salts, sulfonic derivatives of benzothiazoles,benzimidizoles, benzoxazoles and their salts, sulfonic derivatives ofbenzophenone and their salts, sulfonic derivatives of benzylidenecamphor and their salts, derivatives of benzylidene camphor substitutedby a quaternary amine and their salts, derivatives ofphthalydene-camphosulfonic acids and their salts, sulfonic derivativesof benzotriazole, and combinations thereof. Hydrophilic polymers, whichhave light-protective qualities against UV rays, can be used. Theseinclude polymers containing benzylidene camphor and/or benzotriazolegroups.

Suitable liposoluble organic UV filters include derivatives ofpara-aminobenzoic acid, such as the esters or amides ofpara-aminobenzoic acid; derivatives of salicylic acid; derivatives ofbenzophenone; derivatives of dibenzoyl methane; derivatives of diphenylacrylates; derivatives of benzofurans; UV filter polymers containing oneor more silico-organic residues; esters of cinnamic acid; derivatives ofcamphor; derivatives of trianilino-s-triazine; the ethylic esterurocanic acid; benzotriazoles; derivatives of hydroxy phenyl triazine;bis-resorcinol-dialkyl amino triazine; and combinations thereof. Theliposoluble (or lipophilic) organic UV filter can be chosen from octylsalicylate; 4-tert-butyl-4′-methoxy dibenzoyl methane; octocrylene;4-methoxy cinnamate; 2-ethylhexyl [2-ethylhexyl 4-methoxycinnamate]; and2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethyl sily)oxy] disiloxanyl]propynyl] phenol. OtherUV filters that may be useful are derivatives of benzophenones such as2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone, derivatives of benzalmalonates such as polydimethyl/methyl (3(4-(2,2-bis-ethoxy carbonyl vinyl)-phenoxy)-propenyl)siloxane, derivatives of benzylidene camphor such as beta-beta'camphosulfonic [1-4 divinylbenzene] acid and derivatives ofbenzimidazole such as 2-phenyl-benzimidazol-5-sulfonic acid.Water-insoluble UV filters include various mineral oxides. The mineraloxides may be selected from among titanium oxides, zinc oxides, andcerium oxides. The mineral oxides can be used in the form of ultrafinenanoparticles. For example, the UV filters can include Escalol® HP-610(dimethylpabamido propyl laurdimonium tosylate and propylene glycolstearate) or Crodasorb HP (polyquaternium 59).

The antioxidants or antiradical agents can be selected from phenols suchas BHA (tert-butyl-4-hydroxy anisole), BHT (2,6-di-tert-butyl-p-cresol),TBHQ (tert-butyl hydroquinone), polyphenols such as proanthocyanodicoligomers, flavonoids, hindered amines such as tetra amino piperidine,erythorbic acid, polyamines such as spermine, cysteine, glutathione,superoxide dismutase, and lactoferrin.

The vitamins can be selected from ascorbic acid (vitamin C), vitamin E,vitamin E acetate, vitamin E phosphate, B vitamins such as B3 and B5,vitamin PP, vitamin A, and derivatives thereof. The provitamins can beselected from panthenol and retinol.

The protecting agent can be present in an amount from about 0.001% toabout 20% by weight, particularly from about 0.01% to about 10% byweight, and more particularly from 0.1% to about 5% by weight of thetotal weight of the final composition.

The composition of the invention can contain a fixing agent incombination with the above-described polymer. The fixing agent can be ananionic polymer chosen from polymers containing carboxylic units derivedfrom unsaturated carboxylic mono- or polyacids.

The fixing agent can he an amphoteric polymer chosen from the polymercontaining recurring units derived from:

-   -   i. at least one co-repeating unit containing carboxylic acid        units, and    -   ii. at least one basic co-repeating unit, such as esters with        primary, secondary, tertiary, and quaternary amino substituents        of acrylic and methacrylic acids and the product of        quaternization of dimethylaminoethyl methacrylate with dimethyl        or diethyl sulfate.

The fixing agent can be a nonionic polymer chosen frompolyalkyloxazolines; vinyl acetate homopolymers; vinyl acetate andacrylic ester copolymers; vinyl acetate and ethylene copolymers; vinylacetate and maleic ester copolymers; polyethylene and maleic anhydridecopolymers; homopolymers of alkyl acrylates; homopolymers of alkylmethacrylates; copolymers of acrylic esters; copolymers of alkylacrylates and alkyl methacrylates; copolymers of acrylonitrile and anonionic repeating unit chosen from among butadiene and alkyl(meth)acrylates; copolymers of alkyl acrylate and urethane; andpolyamides. The fixing agent can be a functionalized orunfunctionalized, silicone or non-silicone polyurethane. The fixingpolymer can be a polymer of the grafted silicone type containing apolysiloxane portion and a portion consisting of a nonsilicone organicchain, with one of the two portions forming the main chain of thepolymer, and with the other being grafted onto the main chain.

The fixing agent can be present in the composition in a relative weightconcentration between about 0.1% to about 10%, for example, from about0.5% to about 5%.

The personal care/cosmetic composition of the invention can contain anoxidizing agent in combination with the above-described polymer. Theoxidizing agent can be chosen from the group of hydrogen peroxide, ureaperoxide, alkali metal bromates, ferricyanides, persalts, and redoxenzymes, optionally with their respective donor or cofactor. Forexample, the oxidizing agent can be hydrogen peroxide. The oxidizingagent can be a solution of oxygenated water whose titer varies from 1 to40 volumes.

The personal care/cosmetic composition of the invention can contain atleast one reducing agent in combination with the above-described polymerin amounts from about 0.01% to about 30%, particularly from about 0.05%to about 20% of the total weight of the composition. The reducing agentscan be selected from thiols, like cysteine, thioglycolic acid,thiolactic acid, their salts and esters, cysteamine, and its salts orsulfites. In the case of compositions intended for bleaching, ascorbicacid, its salts and its esters, erythorbic acid, its salts and itsesters, and sulfinates, like sodium hydroxymethanesulfinate can be used.

The personal care/cosmetic composition of the invention can contain adye in combination with the above-described polymer. The dye can beselected from the group consisting of neutral acid or cationicnitrobenzene dyes, neutral acid or cationic azo dyes, quinone dyes,neutral, acid or cationic anthraquinone dyes, azine dyes, triarylmethanedyes, indoamine dyes and natural dyes. The dye or dyes can be present ina concentration from about 0.001% to about 20%, and particularly fromabout 0.005% to about 10% based on the total weight of the composition.

In addition, the personal care/cosmetic compositions can include atleast one surfactant in combination with the above-described polymer.The surfactant can be present in an amount from about 0.1% to about 60%,particularly from about 1% to about 40%, and more particularly fromabout 5% to about 30% by weight based on the total weight of thecomposition. The surfactant may be chosen from among anionic,amphoteric, or non-ionic surfactants, or mixtures of them known to beuseful in personal care/cosmetic compositions.

One or more suitable thickeners or viscosity increasing agents may beincluded in combination with the above-described polymer in the personalcare/cosmetic compositions of the invention. Suitable thickeners and/orviscosity increasing agents include: Acetamide MEA;acrylamide/ethalkonium chloride acrylate copolymer;acrylamide/ethyltrimonium chloride acrylate/ethalkonium chlorideacrylate copolymer; acrylamides copolymer; acrylamide/sodium acrylatecopolymer; acrylamide/sodium acryloyldimethyltaurate copolymer;acrylates/acetoacetoxyethyl methacrylate copolymer;acrylates/beheneth-25 methacrylate copolymer; acrylates/C10-C30 alkylacrylate crosspolymer; acrylates/ceteth-20 itaconate copolymer;acrylates/ceteth-20 methacrylate copolymer; acrylates/laureth-25methacrylate copolymer; acrylates/palmeth-25 acrylate copolymer;acrylates/palmeth-25 itaconate copolymer; acrylates/steareth-50 acrylate copolymer; acrylates/steareth-20 itaconate copolymer;acrylates/steareth-20 methacrylate copolymer; acrylates/stearylmethacrylate copolymer; acrylates/vinyl isodecanoate crosspolymer;acrylic acid/acrylonitrogens copolymer; adipic acid/methyl DEAcrosspolymer; agar; agarose; alcaligenes polysaccharides; algin; alginicacid; almondamide DEA; almondamidopropyl betaine; aluminum/magnesiumhydroxide stearate; ammonium acrylates/acrylonitrogens copolymer;ammonium acrylates copolymer; ammonium acryloyldimethyltaurate/vinylformamide copolymer; ammonium acryloyldimethyltaurate/VP copolymer;ammonium alginate; ammonium chloride; ammonium polyacryloyldimethyltaurate; ammonium sulfate; amylopectin; apricotamide DEA;apricotamidopropyl betaine; arachidyl alcohol; arachidyl glycol; arachishypogaea (peanut) flour; ascorbyl methylsilanol pectinate; astragalusgummifer gum; attapulgite; avena sativa (oat) kernel flour; avocadamideDEA; avocadamidopropyl betaine; azelamide MEA; babassuamide DEA; babassuamide MEA; babassuamidopropyl betaine; behenamide DEA; behenamide MEA;behenamidopropyl betaine; behenyl betaine; bentonite; butoxy chitosan;caesalpinia spinosa gum; calcium alginate; calcium carboxymethylcellulose; calcium carrageenan; calcium chloride; calcium potassiumcarbomer; calcium starch octenylsuccinate; C20-40 alkyl stearate;canolamidopropyl betaine; capramide DEA; capryl/capramidopropyl betaine;carbomer; carboxybutyl chitos an; carboxymethyl cellulose acetatebutyrate; carboxymethyl chitin; carboxymethyl chitosan; carboxymethyldextran; carboxymethyl hydroxyethylcellulose; carboxymethylhydroxypropyl guar; carnitine; cellulose acetate propionate carboxylate;cellulose gum; ceratonia siliqua gum; cetearyl alcohol; cetyl alcohol;cetyl babassuate; cetyl betaine; cetyl glycol; cetylhydroxyethylcellulose; chimyl alcohol; cholesterol/HDUpullulancopolymer; cholesteryl hexyl dicarbamate pullulan; citrus aurantiumdulcis (orange) peel extract; cocamide DEA; cocamide MEA; cocamide MIPA;cocamidoethyl betaine; cocamidopropyl betaine; cocamidopropylhydroxysultaine; coco-betaine; coco-hydroxysultaine; coconut alcohol;coco/oleamidopropyl betaine; coco-Sultaine; cocoyl sarcosinamide DEA;cornamide/cocamide DEA; cornamide DEA; croscarmellose; crosslinkedbacillus/glucose/sodium glutamate ferment; cyamopsis tetragonoloba(guar) gum; decyl alcohol; decyl betaine; dehydroxanthan gum; dextrin;dibenzylidene sorbitol; diethanolaminooleamide DEA;diglycol/CHDM/isophthalates/SIP copolymer; dihydroabietyl behenate;dihydrogenated tallow benzylmonium hectorite; dihydroxyaluminumaminoacetate; dimethicone/PEG-10 crosspolymer; dimethicone/PEG-15crosspolymer; dimethicone propyl PG-betaine; dimethylacrylamide/acrylicacid/polystyrene ethyl methacrylate copolymer; dimethylacrylamide/sodiumacryloyldimethyltaurate crosspolymer; disteareth-100 IPDI; DMAPAacrylates/acrylic acid/acrylonitrogens copolymer; erucamidopropylhydroxysultaine; ethylene/sodium acrylate copolymer; gelatin; gellangum; glyceryl alginate; glycine soja (soybean) flour; guarhydroxypropyltrimonium chloride; hectorite; hyaluronic acid; hydratedsilica; hydrogenated potato starch; hydrogenated tallow; hydrogenatedtallowamide DEA; hydrogenated tallow betaine; hydroxybutylmethylcellulose; hydroxyethyl acrylate/sodium acryloyldimethyl tauratecopolymer; hydroxyethylcellulose; hydroxyethyl chitosan; hydroxyethylethylcellulose; hydroxyethyl stearamide-MIPA;hydroxylauryl/hydroxymyristyl betaine; hydroxypropylcellulose;hydroxypropyl chitosan; hydroxypropyl ethylenediamine carbomer;hydroxypropyl guar; hydroxypropyl methylcellulose; hydroxypropylmethylcellulose stearoxy ether; hydroxypropyl starch; hydroxypropylstarch phosphate; hydroxypropyl xanthan gum; hydroxystearamide MEA;isobutylene/sodium maleate copolymer; isostearamide DEA; isostearamideMEA; isostearamide mIPA; isostearamidopropyl betaine; lactamide MEA;lanolinamide DEA; lauramide DEA; lauramide MEA; lauramide MIPA;lauramide/myristamide DEA; lauramidopropyl betaine; lauramidopropylhydroxysultaine; laurimino bispropanediol; lauryl alcohol; laurylbetaine; lauryl hydroxysultaine; lauryl/myristyl glycol hydroxypropylether; lauryl sultaine; lecithinamide DEA; linoleamide DEA; linoleamideMEA; linoleamide MIPA; lithium magnesium silicate; lithium magnesiumsodium silicate; macrocystis pyrifera (kelp); magnesium alginate;magnesium/aluminum/hydroxide/carbonate; magnesium aluminum silicate;magnesium silicate; magnesium trisilicate; methoxy PEG-22/dodecyl glycolcopolymer; methylcellulose; methyl ethylcellulose; methylhydroxyethylcellulose; microcrystalline cellulose; milkamidopropylbetaine; minkamide DEA; minkamidopropyl betaine; MIPA-myristate;montmorillonite; Moroccan lava clay; myristamide DEA; myristamide MEA;myristamide MIPA; myristamidopropyl betaine; myristamidopropylhydroxysultaine; myristyl alcohol; myristyl betaine; natto gum;nonoxynyl hydroxyethylcellulose; oatamide MEA; oatamidopropyl betaine;octacosanyl glycol isostearate; octadecene/MA copolymer; oleamide DEA;oleamide MEA; oleamide MIPA; oleamidopropyl betaine; oleamidopropylhydroxysultaine; oleyl betaine; olivamide DEA; olivamidopropyl betaine;oliveamide MEA; palmamide DEA; palmamide MEA; palmamide MIPA;palmamidopropyl betaine; palmitamide DEA; palmitamide MEA;palmitamidopropyl betaine; palm kernel alcohol; palm kernelamide DEA;palm kernelamide MEA; palm kernelamide MIPA; palm kernelamidopropylbetaine; peanutamide MEA; peanutamide MIPA; pectin; PEG-800;PEG-crosspolymer; PEG-150/decyl alcohol/SMDI copolymer; PEG-175diisostearate; PEG-190 distearate; PEG-15 glyceryl tristearate; PEG-140glyceryl tristearate; PEG-240/HDI copolymer bis-decyltetradeceth-20ether; PEG-100/IPDI copolymer; PEG-180/1aureth-50/TMMG copolymer;PEG-10/lauryl dimethicone crosspolymer; PEG-15/lauryl dimethiconecrosspolymer; PEG-2M; PEG-5M; PEG-7M; PEG-9M; PEG-14M; PEG-20M; PEG-23M;PEG-25M; PEG-45M; PEG-65M; PEG-90M; PEG-115M; PEG-160M; PEG-180M;PEG-120 methyl glucose trioleate; PEG-180/octoxynol-40/TMMG copolymer;PEG-150 pentaerythrityl tetrastearate; PEG-4 rapeseedamide;PEG-150/stearyl alcohol/SMDI copolymer; phaseolus angularis seed powder;polianthes tuberosa extract; polyacrylate-3; polyacrylic acid;polycyclopentadiene; polyether-1; polyethylene/isopropyl maleate/MAcopolyol; polyglyccryl-3 disiloxanc dimethicone; polyglyccryl-3polydimethylsiloxyethyl dimethicone; polymethacrylic acid;polyquaternium-52; polyvinyl alcohol; potassium alginate; potassiumaluminum polyacrylate; potassium carbomer; potassium carrageenan;potassium chloride; potassium palmate; potassium polyacrylate; potassiumsulfate; potato starch modified; PPG-2 cocamide; PPG-1 hydroxyethylcaprylamide; PPG-2 hydroxyethyl cocamide; PPG-2 hydroxyethylcoco/isostearamide; PPG-3 hydroxyethyl soyamide; PPG-14 laureth-60 hexyldicarbamate; PPG-14 laureth-60 isophoryl dicarbamate; PPG-14 palmeth-60hexyl dicarbamate; propylene glycol alginate; PVP/decene copolymer; PVPmontmorillonite; pyrus cydonia seed; pyrus malus (apple) fiber;rhizobian gum; ricebranamide DEA; ricinoleamide DEA; ricinoleamide MEA;ricinoleamide MIPA; ricinoleamidopropyl betaine; ricinoleic acid/adipicacid/AEEA copolymer; rosa multiflora flower wax; sclerotium gum;sesamide DEA; sesamidopropyl betaine; sodium acrylate/acryloyldimethyltaurate copolymer; sodium acrylates/acrolein copolymer; sodiumacrylates/acrylonitrogens copolymer; sodium acrylates copolymer; sodiumacrylates crosspolymer; sodium acrylate/sodium acrylamidomethylpropanesulfonate copolymer; sodium acrylates/vinyl isodecanoate crosspolymer;sodium acrylate/vinyl alcohol copolymer; sodium carbomer; sodiumcarboxymethyl chitin; sodium carboxymethyl dextran; sodium carboxymethylbeta-glucan; sodium carboxymethyl starch; sodium carrageenan; sodiumcellulose sulfate; sodium chloride; sodium cyclodextrin sulfate; sodiumhydroxypropyl starch phosphate; sodium isooctylene/MA copolymer; sodiummagnesium fluorosilicate; sodium oleate; sodium palmitate; sodium palmkernelate; sodium polyacrylate; sodium polyacrylate starch; sodiumpolyacryloyldimethyl taurate; sodium polygamma-glutamate; sodiumpolymethacrylate; sodium polystyrene sulfonate; sodium silicoaluminate;sodium starch octenylsuccinate; sodium stearate; sodium stearoxyPG-hydroxyethylcellulose sulfonate; sodium styrene/acrylates copolymer;sodium sulfate; sodium tallowate; sodium tauride acrylates/acrylicacid/acrylonitrogens copolymer; sodium tocopheryl phosphate; solanumtuberosum (potato) starch; soyamide DEA; soyamidopropyl betaine;starch/acrylates/acrylamide copolymer; starch hydroxypropyltrimoniumchloride; stearamide AMP; stearamide DEA; stearamide DEA-distearate;stearamide DIBA-stearate; stearamide MEA; stearamide MEA-stearate;stearamide MIPA; stearamidopropyl betaine; steareth-60 cetyl ether;steareth-100/PEG-136/HDI copolymer; stearyl alcohol; stearyl betaine;sterculia urens gum; synthetic fluorphlogopite; tallamide DEA; tallowalcohol; tallowamidc DEA; tallowamide MEA; tallowamidopropyl betaine;tallowamidopropyl hydroxysultaine; tallowamine oxide; tallow betaine;tallow dihydroxyethyl betaine; tamarindus indica seed gum; tapiocastarch; TEA-alginate; TEA-carbomer; TEA-hydrochloride; trideceth-2carboxamide MEA; tridecyl alcohol; triethylene glycol dibenzoate;trimethyl pentanol hydroxyethyl ether; triticum vulgare (wheat) germpowder; triticum vulgare (wheat) kernel flour; triticum vulgare (wheat)starch; tromethamine acrylates/acrylonitrogens copolymer; tromethaminemagnesium aluminum silicate; undecyl alcohol; undecylenamide DEA;undecylenamide MEA; undecylenamidopropyl betaine; welan gum; wheatgermamide DEA; wheat germamidopropyl betaine; xanthan gum; yeastbeta-glucan; yeast polysaccharides; zea mays (corn) starch; and blendsthereof.

In one such embodiment, the thickeners or viscosity increasing agentsinclude carbomers, Aculyn™ and Stabileze®, e.g., crosslinked acrylicacid, crosslinked poly(methylvinyl ether/maleic anhydride) copolymer,acrylamides, carboxymethyl cellulose, and the like.

The personal care/cosmetic composition of the invention can contain atleast one amphoteric polymer or a cationic polymer in combination withthe above-described polymer. The cationic or amphoteric polymer orpolymers can be present in an amount from about 0.01% to about 10%,particularly from about 0.05% to about 5%, and more particularly fromabout 0.1% to about 3% by weight of the total weight of the composition.

For some embodiments, it may be preferred to add one or morepreservatives and/or antimicrobial agents, such as, but not limited to,benzoic acid, sorbic acid, dehydroacetic acid, piroctone olamine, DMDMhydantoin, IPBC, triclosan, bronopol, formaldehyde, isothiazolinones,nitrates/nitrites, parabens, phenoxyethanol, potassium sorbate, sodiumbenzoate, sulphites, and sulphur dioxide. Combinations of preservativesmay be used.

In other embodiments it may be desirable to incorporate preservativeboosters/solvents, select examples of which include caprylyl glycol,hexylene glycol, pentylene glycol, ethylhexylglycerin, caprylhydroxamicacid, and glyceryl caprylate.

In other embodiments it may be desirable to include one or more otheringredients, such as synthetic and natural oils and waxes. The syntheticoils include polyolefins, e.g., poly-α-olefins such as polybutenes,polyisobutenes and polydecenes. The polyolefins can be hydrogenated. Themineral oils suitable for use in the compositions of the inventioninclude hexadecane and oil of paraffin. Suitable animal and vegetableoils include sunflower, corn, soy, avocado, jojoba, squash, raisin seed,sesame seed, walnut oils, fish oils, glycerol tricaprocaprylate,Purcellin oil or liquid jojoba. Suitable natural or synthetic oilsinclude eucalyptus, lavender, vetiver, litsea cubeba, lemon, sandalwood,rosemary, chamomile, savory, nutmeg, cinnamon, hyssop, caraway, orange,geranium, cade, and bergamot. Suitable natural and synthetic waxesinclude carnauba wax, candelila wax, alfa wax, paraffin wax, ozokeritewax, vegetable waxes such as olive wax, rice wax, hydrogenated jojobawax, absolute flower waxes such as black currant flower wax, animalwaxes such as bees wax, modified bees wax (cerabellina), marine waxesand polyolefin waxes such as polyethylene wax.

The personal care/cosmetic compositions may be used to wash and treatkeratinous material such as hair, skin, eyelashes, eyebrows,fingernails, lips, and hairy skin. The invention provides a method fortreating keratinous material including the skin or hair, by applying toskin or keratinous materials a personal care/cosmetic composition asdescribed above, and then eventually rinsing it with water. Accordingly,the method makes it possible to maintain the hairstyle, treatment, care,washing, or make-up removal of the skin, the hair, and any otherkeratinous material.

The personal care/cosmetic compositions described herein are useful inpersonal care/cosmetic products, including, but not limited to, gels,lotions, glazes, glues, mousses, sprays, fixatives, shampoos,conditioners, 2-in-1 shampoos, temporary hair dyes, semi-permanent hairdyes, permanent hair dyes, straighteners, permanent waves, relaxers,creams, putties, waxes, pomades, moisturizers, mascaras, lip balms andfoam enhancers. The personal care/cosmetic compositions can be detergentcompositions such as shampoos, bath gels, and bubble baths. In thismode, the compositions will comprise a generally aqueous washing base.The surfactant or surfactants that form the washing base may be chosenalone or in blends, from known anionic, amphoteric, or non-ionicsurfactants. The quantity and quality of the washing base must besufficient to impart a satisfactory foaming and/or detergent value tothe final composition. The washing base can be from about 4% to about50% by weight, particularly from about 6% to about 35% by weight, andeven more particularly from about 8% to about 25% by weight of the totalweight of the final composition. The personal care/cosmetic compositionsmay also take the form of after-shampoo compositions, to be rinsed offor not, for permanents, straightening, waving, dyeing, or bleaching, orthe form of rinse compositions to be applied before or after dyeing,bleaching, permanents, straightening, relaxing, waving or even betweenthe two stages of a permanent or straightening process. The personalcare/cosmetic compositions may also take the form of skin-washingcompositions, and particularly in the form of solutions or gels for thebath or shower, or of make-up removal products. The personalcare/cosmetic compositions may also be in the form of aqueous orhydro-alcoholic solutions for skin and/or hair care.

The pH of the composition applied to the keratinous material isgenerally between 2 and 12. In one embodiment, the pH is from about 3 toabout 8, and may he adjusted to the desired value by means of acidifyingor alkalinizing agents that are well known in the state of the art.Thus, the composition of the invention can contain at least onealkalizing or acidifying agent in amounts from about 0.01% to about 30%based on the total weight of the composition.

The alkalizing agent can be chosen from ammonia, alkali hydroxides,alkali carbonates, alkanolamines, like mono-, di- and triethanolamines,as well as their derivatives, hydroxyalkylamines and ethoxylated and/orpropoxylated ethylenediamines, unsubstituted and substitutedpropylenediamines.

The acidifying agent can be chosen from mineral or organic acids, likehydrochloric acid, orthophosphoric acid, carboxylic acids like tartaricacid, citric acid, or lactic acid, or sulfonic acids, and the like.

The personal care/cosmetic compositions of the invention may include aphysiological and cosmetically acceptable medium. Such medium mayconsist exclusively of water, a cosmetically acceptable solvent, or ablend of water and a cosmetically acceptable solvent, such as a loweralcohol composed of C 1 to C4, such as ethanol, isopropanol, t-butanol,n-butanol, alkylene glycols such as propylene glycol, and glycol ethers.Alternatively, the personal care/cosmetic compositions can be anhydrous.

Generally, personal care/cosmetic compositions can be prepared by simplemixing procedures well known in the art.

The invented polymers can be prepared according to the examples set outbelow. The examples are presented for purposes of demonstrating, but notlimiting, the preparation of the compounds and compositions of thisinvention.

EXAMPLES

The following non-limiting examples are provided to illustrate a fewmethods for preparing multifunctional polymers.

Example 1 Synthesis of 16% N-(3-dimethylaminopropyl) methacrylamide/20%butyl methacrylate/64% N-vinyl pyrrolidone (molar ratios) terpolymer

Isopropanol (204.0 g), N-vinyl pyrrolidone (VP) (23.47 g),N-(3-dimethylaminopropyl) methacrylamide (DMAPMA) (1.80 g), and butylmethacrylate (BMA) (1.88 g) were loaded into a glass kettle reactor. Themixture was purged with nitrogen and then heated under nitrogen to 81°C. with stirring at 200 rpm. Meanwhile, a repeating unit premix wasprepared with 96.00 g of isopropanol, 7.19 g of DMAPMA, and 7.51 g ofBMA. At t=0, 0.14 g of Trigonox® 25C75 (AkzoNobel, t-butylperoxy-pivalate initiator) was charged into the reactor. The repeatingunit premix was emptied into the reactor at a constant rate in 3 hours.Additional shots of Trigonox® 25C75 were added at t=1, 2, 3 hour (0.14 geach) and t=4, 6 hour (0.56 g each). After the last initiator addition,the reactor was kept stirring at 81° C. for 1 hour. The polymer solutionwas then cooled and discharged.

Example 2 Synthesis of 12% N-(3-dimethylaminopropyl) methacrylamide/40%butyl methacrylate/48% N-vinyl pyrrolidone (molar ratios) terpolymer

Isopropanol (184.0 g), VP (16.0 g), DMAPMA (1.23 g), and BMA (3.41 g)were loaded into a glass kettle reactor. The mixture was purged withnitrogen and then heated under nitrogen to 82° C. with stirring at 200rpm. Meanwhile, a repeating unit premix was prepared with 96.00 g ofisopropanol, 4.90 g of DMAPMA, and 13.65 g of BMA. At t=0, 0.13 g ofTrigonox® 25C75 (AkzoNobel, t-butyl peroxy-pivalate initiator) wascharged into the reactor. The repeating unit premix was emptied into thereactor at a constant rate in 3 hours. Additional shots of Trigonox®25C75 were added at t=1, 2, 3 hour (0.13 g each) and t=4, 6 hour (0.53 geach). After the last initiator addition, the reactor was kept stirringat 82° C. for 1 hour. The polymer solution was then cooled anddischarged.

Example 3 Synthesis 40% N-(3-dimethylaminopropyl) methacrylamide/20%butyl methacrylate/of 40% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 338.00 g of isopropanol, 22.23 g of VP, 6.81 g of DMAPMA,and 2.84 g of BMA were loaded into a glass kettle reactor. The mixturewas purged with nitrogen and then heated under nitrogen to 80° C. withstirring at 200 rpm. Meanwhile, a repeating unit premix was preparedwith 152.00 g of isopropanol, 27.24 g of DMAPMA, and 11.38 g of BMA. Att=0, 0.25 g of Trigonox® 25C75 (AkzoNobel, t-butyl peroxy-pivalateinitiator) was charged into the reactor. The repeating unit premix wasemptied into the reactor at a constant rate in 3 hours. Additional shotsof Trigonox® 25C75 were added at t=1, 2, 3 hour (0.25 g each) and t=4, 6hour (1.00 g each). After the last initiator addition, the reactor waskept stirring at 80° C. for 1 hour. The polymer solution was then cooledand discharged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.13. Part of the polymer solutionwas then neutralized by 1 M HCl solution (1:1 molar of DMAPMA). Theisopropanol was removed by solvent exchange with water. The water wasthen removed by vacuum stripping and a slightly yellow, fine powder wasresulted. The polymer was found to give clear solutions in water forconcentration at least up to and including 10% by weight.

Example 4 Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40%butyl methacrylate/30% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 338.00 g of isopropanol, 16.67 g of VP, 5.11 g of DMAPMA,and 5.69 g of BMA were loaded into a glass kettle reactor. The mixturewas purged with nitrogen and then heated under nitrogen to 80° C. withstirring at 200 rpm. Meanwhile, a repeating unit premix was preparedwith 152.00 g of isopropanol, 20.43 g of DMAPMA, and 22.75 g of BMA. Att=0, 0.25 g of Trigonox® 25C75 (AkzoNobel, t-butyl peroxy-pivalateinitiator) was charged into the reactor. The repeating unit premix wasemptied into the reactor at a constant rate in 3 hours. Additional shotsof Trigonox® 25C75 were added at t=1, 2, 3 hour (0.25 g each) and t=4, 6hour (1.00 g each). After the last initiator addition, the reactor waskept stirring at 80° C. for 1 hour. The polymer solution was then cooledand discharged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.12. Part of the polymer solutionwas then neutralized by 1 M HC1 solution (1:1 molar of DMAPMA). Theisopropanol was removed by solvent exchange with water. The water wasthen removed by vacuum stripping and a slightly yellow, fine powder wasresulted. The polymer was found to give clear solutions in water forconcentration at least up to and including 5% by weight. A 10% (w/w)solution in water sometimes was slightly hazy.

Example 5 Synthesis of 64% N-(3-dimethylaminopropyl) methacrylamide/20%butyl methacrylate/16% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 338.00 g of isopropanol, 8.89 g of VP, 10.90 g of DMAPMA,and 2.84 g of BMA were loaded into a glass kettle reactor. The mixturewas purged with nitrogen and then heated under nitrogen to 83° C. withstirring at 200 rpm. Meanwhile, a repeating unit premix was preparedwith 152.00 g of isopropanol, 43.58 g of DMAPMA, and 11.38 g of BMA. Att=0, 0.25 g of Trigonox® 25C75 (AkzoNobel, t-butyl peroxy-pivalateinitiator) was charged into the reactor. The repeating unit premix wasemptied into the reactor at a constant rate in 3 hours. Additional shotsof Trigonox® 25C75 were added at t=1, 2, 3 hour (0.25 g each) and t=4, 6hour (1.00 g each). After the last initiator addition, the reactor waskept stirring at 83° C. for 1 hour. The polymer solution was then cooledand discharged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.10. Part of the polymer solutionwas then neutralized by 1 M HCl solution (1:1 molar of DMAPMA). Theisopropanol was removed by solvent exchange with water. The water wasthen removed by vacuum stripping and a slightly yellow, fine powder wasresulted.

Example 6 Synthesis of 48% N-(3-dimethylaminopropyl) methacrylamide/40%butyl methacrylate/12% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 338.00 g of isopropanol, 6.67 g of VP, 8.17 g of DMAPMA,and 5.69 g of BMA were loaded into a glass kettle reactor. The mixturewas purged with nitrogen and then heated under nitrogen to 83° C. withstirring at 200 rpm. Meanwhile, a repeating unit premix was preparedwith 152.00 g of isopropanol, 32.69 g of DMAPMA, and 22.75 g of BMA. Att=0, 0.25 g of Trigonox® 25C75 (AkzoNobel, t-butyl peroxy-pivalateinitiator) was charged into the reactor. The repeating unit premix wasemptied into the reactor at a constant rate in 3 hours. Additional shotsof Trigonox® 25C75 were added at t=1, 2, 3 hour (0.25 g each) and t=4, 6hour (1.00 g each). After the last initiator add ition, the reactor waskept stirring at 83° C. for 1 hour. The polymer solution was then cooledand discharged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.10. Part of the polymer solutionwas then neutralized by 1 M HCl solution (1:1 molar of DMAPMA). Theisopropanol was removed by solvent exchange with water. The water wasthen removed by vacuum stripping and a slightly yellow, fine powder wasresulted.

Molecular weights were measured as a 0.15% polymer solution inmethanol/water mobile phase in using PEO/PEG standards. M_(w) was foundto be 2,640 Da, and M_(n) was determined to be 1,170 Da.

Example 7 Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40%butyl methacrylate/30% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 30.00 g of ethanol, 33.34 g of VP, 10.22 g of DMAPMA, and11.38 g of BMA were loaded into an Autoclave Engineers' reactor. Themixture was purged with nitrogen and then heated under nitrogen to 116°C. with stirring at 200 rpm. Meanwhile, a pump was filled with a mixtureof 64.00 g of ethanol, 40.86 g of DMAPMA, and 45.50 g of BMA. At t=0,0.58 g of Trigonox® 121 (AkzoNobel, t-amyl peroxy-2-ethylhexanoateinitiator) was charged into the reactor. Then the contents of the pumpwere emptied into the reactor at a constant rate over the next 3 hours.Additional 12 shots of Trigonox® 121 were added into the reactor every15 min (0.58 g each). Then the reaction was cooled to 92° C. Starting att=4 hour, 6 shots of Trigonox® 121 were added into the reactor everyhour (1.17 g each). After the last initiator addition, the reactor waskept stirring at 92° C. for 3 hours. The polymer solution was thencooled and discharged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.11. Part of the polymer solutionwas then neutralized by 1 M HCl solution (1:1 molar of DMAPMA). Theethanol was removed by solvent exchange with water. The water was thenremoved by vacuum stripping and a slightly yellow, fine powder wasresulted.

Molecular weights were measured as a 0.15% polymer solution inmethanol/water mobile phase in using PEO/PEG standards. M_(w) was foundto be 5,000 Da, and M_(n) was determined to be 826 Da.

Example 8 Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40%butyl methacrylate/30% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 130.00 g of ethanol, 33.34 g of VP, 25.54 g of DMAPMA, and11.38 g of BMA were loaded into an Autoclave Engineers' reactor. Themixture was purged with nitrogen and then heated to 116° C. undernitrogen with stirring at 200 rpm. Meanwhile, a pump was filled with amixture of 64.00 g of ethanol, 25.54 g of DMAPMA, and 45.50 g of BMA. Att=0, 0.58 g of Trigonox® 121 (AkzoNobel, t-amyl peroxy-2-ethylhexanoateinitiator) was charged into the reactor. Then the contents of the pumpwere emptied into the reactor at a constant rate over the next 3 hours.Additional 12 shots of Trigonox® 121 were added into the reactor every15 min (0.58 g each). Then the reaction was cooled to 92° C. Starting att=4 hour, 5 shots of Trigonox® 121 were added into the reactor everyhour (1.17 g each for the first 4 shots and 2.33 g for the last shot).After the last initiator addition, the reactor was kept stirring at 92°C. for 3 hours. The polymer solution was then cooled and discharged.Part of the polymer solution was then neutralized by 1 M HCl solution(1:1 molar of DMAPMA). The ethanol was removed by solvent exchange withwater. The water was then removed by vacuum stripping and a slightlyyellow, fine powder was resulted.

Molecular weights were measured as a 0.15% polymer solution inmethanol/water mobile phase in using PEO/PEG standards. M_(w) was foundto be 8,250 Da, and M_(n) was determined to be 1,180 Da.

Example 9 Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40%butyl methacrylate/30% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 200.00 g of ethanol, 33.34 g of VP, 10.22 g of DMAPMA, and1 L38 g of BMA were loaded into a glass kettle reactor. The mixture waspurged with nitrogen and then heated to 80° C. under nitrogen withstirring at 200 rpm. Meanwhile, a repeating unit premix was preparedwith 40.86 g of DMAPMA and 45.50 g of BMA. Starting at t=0, 1.70 g ofTrigonox® 121 (AkzoNobel, t-amyl peroxy-2-ethylhexanoate initiator) wascharged into the reactor in 3 hours and the contents of the repeatingunit premix were also emptied into the reactor at a constant rate overthe 3 hours. Starting at t=5 hour, additional 2.85 g of Trigonox® 121was added into the reactor over 2 hours. Then the reactor was keptstirring at 80° C. for 1 hour. The polymer solution was then cooled anddischarged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.29.

Example 10 Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40%butyl methacrylate/30% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 85.00 g of ethanol, 33.34 g of VP, 10.22 g of DMAPMA, and11.38 g of BMA were loaded into a glass kettle reactor. The mixture waspurged with nitrogen and then heated to 80° C. under nitrogen withstirring at 200 rpm. Meanwhile, a repeating unit premix was preparedwith 40.86 g of DMAPMA and 45.50 g of BMA. Starting at t=0, 0.85 g ofTrigonox® 121 (AkzoNobel, t-amyl peroxy-2-cthylhcxanoatc initiator) wascharged into the reactor in 3 hours and the contents of the repeatingunit premix were also emptied into the reactor at a constant rate overthe 3 hours. Starting at t=5 hour, additional 2.85 g of Trigonox® 121was added into the reactor over 2 hours. Then the reactor was keptstirring at 80° C. for 1 hour. The polymer solution was then cooled anddischarged.

Molecular weights were measured as a 0.15% polymer solution inmethanol/water mobile phase in using PEO/PEG standards. M_(w) was foundto be 21,400 Da, and M_(n) was determined to be 5,220 Da.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.97.

Example 11 Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40%2-ethylhexyl methacrylate/30% N-vinyl pyrrolidone (molar ratios)terpolymer

A quantity of 130.00 g of ethanol, 28.34 g of VP, 21.71 g of DMAPMA, and13.48 g of 2-ethylhexyl methacrylate (EHMA) were loaded into anAutoclave Engineers' reactor. The mixture was purged with nitrogen andthen heated to 116° C. under nitrogen with stirring at 200 rpm.Meanwhile, a pump was filled with a mixture of 64.00 g of ethanol, 21.71g of DMAPMA, and 53.94 g of EIIMA. At t=0, 0.57 g of Trigonox® 121(AkzoNobel, t-amyl peroxy-2-ethylhexanoate initiator) was charged intothe reactor. Then the contents of the pump were emptied into the reactorat a constant rate over the next 3 hours. Additional Trigonox® 121 wascharged into the reactor over 2.75 hours (6.83 g). Then the reaction wascooled to 91° C. Starting at t=4 hour, 4 shots of Trigonox® 121 wereadded into the reactor every hour (1.75 g each). After the lastinitiator addition, the reactor was kept stirring at 91° C. for 3 hours.The polymer solution was then cooled and discharged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.10. Part of the polymer solutionwas then neutralized by 1 M HC1 solution (1:1 molar of DMAPMA). Theethanol was removed by solvent exchange with water. The water was thenremoved by vacuum stripping and a slightly yellow, fine powder wasresulted. The polymer was found to give a hazy solution at 1% weightaddition in water. Cloudy solutions were produced in water for solutionscontaining 2.5% to 10% (w/w) polymer.

Molecular weights were measured as a 0.15% polymer solution inmethanol/water mobile phase in using PEO/PEG standards. M_(w) was foundto be 2,280 Da, and M_(n) was determined to be 686 Da.

Example 12 Synthesis of 40% N-(3-dimethylaminopropyl) methacrylamide/20%2-ethylhexyl methacrylate/40% N-vinyl pyrrolidone (molar ratios)terpolymer

A quantity of 130.00 g of ethanol, 37.79 g of VP, 28.94 g of DMAPMA, and6.74 g of EIIMA were loaded into an Autoclave Engineers' reactor. Themixture was purged with nitrogen and then heated to 116° C. undernitrogen with stirring at 200 rpm. Meanwhile, a pump was filled with amixture of 45.00 g of ethanol, 28.94 g of DMAPMA, and 26.98 g of EHMA.Starting at t=0, 6.90 g of Trigonox® 121 (AkzoNobel, t-amylperoxy-2-ethylhexanoate initiator) was charged into the reactor over 3hours. The contents of the pump were also emptied into the reactor at aconstant rate in 3 hours. Then the reaction was cooled to 91° C.Starting at t=4 hour, 5 shots of Trigonox® 121 were added into thereactor every hour (1.30 g each). After the last initiator addition, thereactor was kept stirring at 91° C. for 3 hours. The polymer solutionwas then cooled and discharged. The relative viscosity was measured fora 1% (wt/v) polymer solution in ethanol at 25° C., and found to be 1.20.Part of the polymer solution was then neutralized by 1 M HCl solution(1:1 molar of DMAPMA). The ethanol was removed by solvent exchange withwater. The water was then removed by vacuum stripping and a slightlyyellow, fine powder was resulted.

Molecular weights were measured as a 0.15% polymer solution inmethanol/water mobile phase in using PEO/PEG standards. M_(w) was foundto be 13,100 Da, and M_(n) was determined to be 1,250 Da.

Example 13 Synthesis of 16% N-(3-dimethylaminopropyl) methacrylamide/20%lauryl methacrylate/64% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 159.00 g of isopropanol, 17.78 g of VP, 1.36 g of DMAPMA,and 2.54 g of lauryl methacrylate (LMA) were loaded into a glass kettlereactor. The mixture was purged with nitrogen and then heated to 82° C.under nitrogen with stirring at 200 rpm. Meanwhile, a repeating unitpremix was prepared with 36.00 g of isopropanol, 5.45 g of DMAPMA, and10.18 g of LMA. At t=0, 0.125 g of Trigonox® 25C75 (AkzoNobel, t-butylperoxy-pivalate initiator) was charged into the reactor. The repeatingunit premix was emptied into the reactor at a constant rate in 3 hours.Additional shots of Trigonox® 25C75 was added at t=1, 2, 3 hour (0.125 geach) and t=4, 5, 6, 7 hour (0.25 g each). After the last initiatoraddition, the reactor was kept stirring at 82° C. for 1 hour. Thepolymer solution was then cooled and discharged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.13. Part of the polymer solutionwas then neutralized by 1 M HCl solution (1:1 molar of DMAPMA). Theisopropanol was removed by solvent exchange with water. The water wasthen removed by vacuum stripping and a slightly yellow, fine powder wasresulted.

Example 14 Synthesis of 12% N-(3-dimethylaminopropyl) methacrylamide/40%lauryl methacrylate/48% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 170.00 g of isopropanol, 13.34 g of VP, 1.02 g of DMAPMA,and 5.09 g of LMA were loaded into a glass kettle reactor. The mixturewas purged with nitrogen and then heated to 81° C. under nitrogen withstirring at 200 rpm. Meanwhile, a repeating unit premix was preparedwith 80.00 g of isopropanol, 4.09 g of DMAPMA, and 20.36 g of LMA. Att=0, 0.125 g of Trigonox® 25C75 (AkzoNobel, t-butyl peroxy-pivalateinitiator) was charged into the reactor. The repeating unit premix wasemptied into the reactor at a constant rate in 3 hours. Additional shotsof Trigonox® 25C75 were added at t=1, 2, 3 hour (0.125 g each) and t=4,5, 6, 7 hour (0.25 g each). After the last initiator addition, thereactor was kept stirring at 81° C. for 1 hour. The polymer solution wasthen cooled and discharged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.12. Part of the polymer solutionwas then neutralized by 1 M HCl solution (1:1 molar of DMAPMA). Theisopropanol was removed by solvent exchange with water. The water wasthen removed by vacuum stripping and a slightly yellow, fine powder wasresulted.

Example 15 Synthesis of 40% N-(3-dimethylaminopropyl) methacrylamide/20%lauryl methacrylate/40% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 165.00 g of isopropanol, 11.11 g of VP, 3.41 g of DMAPMA,and 2.54 g of LMA were loaded into a glass kettle reactor. The mixturewas purged with nitrogen and then heated to 80° C. under nitrogen withstirring at 200 rpm. Meanwhile, a repeating unit premix was preparedwith 60.00 g of isopropanol, 13.62 g of DMAPMA, and 10.18 g of LMA. Att=0, 0.125 g of Trigonox® 25C75 (AkzoNobel, t-butyl peroxy-pivalateinitiator) was charged into the reactor. The repeating unit premix wasemptied into the reactor at a constant rate in 3 hours. Additional shotsof Trigonox® 25C75 were added at t=1, 2, 3 hour (0.125 g each) and t=4,5, 6, 7 hour (0.25 g each). After the last initiator addition, thereactor was kept stirring at 80° C. for 1 hour. The polymer solution wasthen cooled and discharged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.12. Part of the polymer solutionwas then neutralized by 1 M HCl solution (1:1 molar of DMAPMA). Theisopropanol was removed by solvent exchange with water. The water wasthen removed by vacuum stripping and a slightly yellow, fine powder wasresulted.

Example 16 Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40%lauryl methacrylate/30% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 199.00 g of isopropanol, 8.34 g of VP, 2.55 g of DMAPMA,and 5.09 g of LMA were loaded into a glass kettle reactor. The mixturewas purged with nitrogen and then heated to 82° C. under nitrogen withstirring at 200 rpm. Meanwhile, a repeating unit premix was preparedwith 76.00 g of isopropanol, 10.22 g of DMAPMA, and 20.35 g of LMA. Att=0, 0.125 g of Trigonox® 25C75 (AkzoNobel, t-butyl peroxy-pivalateinitiator) was charged into the reactor. The repeating unit premix wasemptied into the reactor at a constant rate in 3 hours. Additional shotsof Trigonox® 25C75 were added at t=1, 2, 3 hour (0.125 g each) and t=4,5, 6, 7 hour (0.25 g each). After the last initiator addition, thereactor was kept stirring at 82° C. for 1 hour. The polymer solution wasthen cooled and discharged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.11. Part of the polymer solutionwas then neutralized by 1 M HCl solution (1:1 molar of DMAPMA). Theisopropanol was removed by solvent exchange with water. The water wasthen removed by vacuum stripping and a slightly yellow, fine powder wasresulted.

Example 17 Synthesis of 64% N-(3-dimethylaminopropyl) methacrylamide/20%lauryl methacrylate/16% N-vinyl pyrrolidone (molar ratios) tcrpolymcr

A quantity of 130.00 g of isopropanol, 4.45 g of VP, 5.45 g of DMAPMA,and 2.54 g of LMA were loaded into a glass kettle reactor. The mixturewas purged with nitrogen and then heated to 83° C. under nitrogen withstirring at 200 rpm. Meanwhile, a repeating unit premix was preparedwith 120.00 g of isopropanol, 21.79 g of DMAPMA, and 10.18 g of LMA. Att=0, 0.125 g of Trigonox® 25C75 (AkzoNobel, t-butyl peroxy-pivalateinitiator) was charged into the reactor. The repeating unit premix wasemptied into the reactor at a constant rate in 3 hours. Additional shotsof Trigonox® 25C75 were added at t=1, 2, 3 hour (0.125 g each) and t=4,5, 6, 7 hour (0.25 g each). After the last initiator addition, thereactor was kept stirring at 83° C. for 1 hour. The polymer solution wasthen cooled and discharged

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.13. Part of the polymer solutionwas then neutralized by 1 M HCl solution (1:1 molar of DMAPMA). Theisopropanol was removed by solvent exchange with water. The water wasthen removed by vacuum stripping and a slightly yellow, fine powder wasresulted.

Example 18 Synthesis of 48% N-(3-dimethylaminopropyl) methacrylamide/40%lauryl methacrylate/12% N-vinyl pyrrolidone (molar ratios) terpolymer

A quantity of 140.00 g of isopropanol, 3.33 g of VP, 4.09 g of DMAPMA,and 5.09 g of LMA were loaded into a glass kettle reactor. The mixturewas purged with nitrogen and then heated to 83° C. under nitrogen withstirring at 200 rpm. Meanwhile, a repeating unit premix was preparedwith 160.00 g of isopropanol, 16.34 g of DMAPMA, and 20.35 g of LMA. Att=0, 0.125 g of Trigonox® 25C75 (AkzoNobel, t-butyl peroxy-pivalateinitiator) was charged into the reactor. The repeating unit premix wasemptied into the reactor at a constant rate in 3 hours. Additional shotsof Trigonox® 25C75 were added at t=1, 2, 3 hour (0.125 g each) and t=4,5, 6, 7 hour (0.25 g each). After the last initiator addition, thereactor was kept stirring at 83° C. for 1 hour. The polymer solution wasthen cooled and discharged.

The relative viscosity was measured for a 1% (wt/v) polymer solution inethanol at 25° C., and found to be 1.09. Part of the polymer solutionwas then neutralized by 1 M HCl solution (1:1 molar of DMAPMA). Theisopropanol was removed by solvent exchange with water. The water wasthen removed by vacuum stripping and a slightly yellow, fine powder wasresulted.

Comparative Example 1 Antimicrobial Activity of Repeating Units ViaStreak Plate Method

The antimicrobial activity of N-vinyl-2-pyrrolidone (VP),dimethylaminopropyl methacrylamide (DMAPMA), and butyl methacrylate(BMA)were evaluated using a streak plate method. Briefly, stock solutionof each microorganism was prepared by growing the bacterial cells intryptic soy broth (TSB) or the fungi cells in yeast malt broth (YM) toreach a concentration of about 10⁸-10⁹ cfu/mL. Molten agar (TSA or YM)was seeded with each microorganism to obtain a microbial concentrationof about 10⁵-10⁶ cfu/mL. Plates were allowed to solidify. Monomer plateswere challenged with the following microbes: Staphylococcus aureus (ATCC6538), Escherichia coli (ATCC 8730), Pseudomonas aeruginosa (ATCC 9027),Candida albicans (ATCC 10231) and Aspergillus niger (ATCC 16404). Therepeating units were tested as a 1% solution in water, and DMAPMAsolution was adjusted to pH 6-7 prior to testing. The plates wererefrigerated for 24 hours to allow for the polymer to diffuse and werethen placed in the incubator (32° C. for bacteria plates, 28° C. forfungal plates) for 24-72 hrs. Growth inhibition along the polymericstreak or polymer sprinkles was considered as indicative ofantimicrobial activity. Seeded plates without polymers were used aspositive controls for microbial growth.

No repeating unit showed antimicrobial activity for the microbes tested.

Example 19 Antimicrobial Testing Via Plate Streak Method

The antimicrobial activity of the various polymers was evaluated using aplate streak method. The method of the Comparative Example was followed,except polymers were tested either as a 5% solution in water or aspowders by streaking the solution or sprinkling the polymers over themicrobial seeded plate, respectively. The results of the streak test forvarious polymers are summarized in the Table 1 below. A “−” symbolindicates that antimicrobial activity was observed (growth inhibition)whereas a “+” symbol indicates that no antimicrobial activity wasdetected in this assay.

TABLE 1 Microbial test results of Example 19 growth inhibition S. E. P.A. C. polymer aureus coli aeruginosa niger albicans Example 3 − − − + +Example 4 − − − + + Example 5 − − − + + Example 6 − − − + + Example 7− + + + + Example 8 − − − + + Example 11 − − + + + Example 12 − + + − −Example 13 + + + + + Example 14 + + + + + Example 15 − + + + + Example16 − + + + + Example 17 − + + + + Example 18 − + + + +

As shown in the Table 1 above, multifunctional polymers embraced by theinvention showed antimicrobial activity.

Example 20

The antimicrobial activity of selected polymers was further evaluated bya shake flask method. Briefly, 2% by wt. of the polymers were added toTSB. The pH of the media was adjusted to a pH of about 6. Each flask wasthen inoculated with a microorganism to achieve an initial concentrationof about 10⁶ cfu/mL and incubated with shaking at 32° C. Microbialcounts were conducted after 48 hours by serially diluting and platingonto TSA media. The log reduction values (Log CFIJ/mL control at t=48h—Log CFIJ/mL treated sample at t =48 hours) of the polymer in Example 8tested against S. aureus, E. coli and P. aeruginosa were >7.2, >7.2, and6.0, respectively. Therefore, the antimicrobial activity of Example 8polymer when tested at 2% resulted in total growth inhibition of both S.aureus and E. coli.

Example 21 Compatibility with Formulation Polymers

The poly(DMAPMA/BMA/VP) multifunctional polymer of Examples 8wasevaluated for compatibility with four formulation polymers:polyquaternium-69 (Aquastyle™ 300AF, Ashland Specialty Ingredients),polyimide-1 (Aquaflex™ XL30, Ashland Specialty Ingredients), andpolyquaternium-55 (Styleze™ W20, Ashland Specialty Ingredients). Toevaluate compatibility a total of twenty-five 10 gram samples consistingof a ranging amount of candidate polymer, existing product and waterwere prepared. Then, 1-5% of the candidate polymer (based on 10 g totalsample) was mixed with 1-5% of existing product (based on 10 g totalsample) and water was added to bring total mass of sample to ten grams.Amount of all constituent components were adjusted to reflect percentsolids.

Overall, the polymer showed good compatibility with the formulationpolymers (Tables 2). In the case of polyquaternium-69 and polyimide-1,clear solutions existed at virtually all evaluated levels, with onlyslight haze at the highest concentrations, were observed (Tables 2).With polyquaternium-5 5 clear solutions were observed until 2-3% of themultifunctional polymer and existing product (Table 2).

TABLE 2 Compatibility of 30% VP/30% DMAPMA/40% BMA (molar ratios) withformulation polymers. formulation multifunctional polymer addition level(w/w) polymer 1% 2% 3% 4% 5% pH polyquaternium-69 1% clear clear clearclear clear 5-6 2% clear clear clear clear clear 3% clear clear clearclear clear 4% clear clear clear clear clear 5% clear clear clear clearclear polyimide-1 1% clear clear clear clear clear 6.5-7.5 2% clearclear clear clear clear 3% clear clear clear clear clear 4% clear clearclear clear slightly hazy 5% clear clear clear clear slightly hazypolyquaternium-55 1% clear clear clear clear clear 4.5-5.0 2% clearclear clear clear slightly hazy 3% clear clear slightly slightly hazyhazy hazy 4% clear clear slightly slightly hazy hazy hazy 5% clear clearslightly slightly hazy hazy hazy

While a number of embodiments of this invention have been represented,it was apparent that the basic construction can be altered to provideother embodiments that utilize the invention without departing from thespirit and scope of the invention. All such modifications and variationsare intended to be included within the scope of the invention as definedin the appended claims rather than the specific embodiments that havebeen presented by way of example.

1-13. (canceled)
 14. A terpolymer having structure

wherein: R₁ and R₄ are independently selected from the group consistingof hydrogen, methyl, and combinations thereof, R₂ and R₃ areindependently selected C1-C20 alkyl, R₅ is selected from the groupconsisting of functionalized and unfunctionalized alkyl, alkoxy,cycloalkyl, alkenyl, and aryl, R₆ and R₇ are selected from the groupconsisting of functionalized and unfunctionalized alkyl, alkoxy,cycloalkyl, alkenyl, and aryl, and wherein R₆ and R₇ may form a 5 to7-membered ring, Q is selected from the group consisting offunctionalized and unfunctionalized alkylene, alkyleneoxy,cycloalkylene, alkenylene, and arylene, X is O, NH, or combinationsthereof, and a, b, and c are molar ratios equaling 100%.
 15. Theterpolymer according to claim 14 wherein said a ranges from about 5% toabout 80%, said b ranges from about 5% to about 60%, and said c rangesfrom about 5% to about 80% (all molar ratios).
 16. (canceled)
 17. Theterpolymer according to claim 14, wherein said terpolymer exhibitsantimicrobial activity against a microbe selected from the groupconsisting of S. aureus, E. coli, P. aeruginosa, A. niger, C. albicans,and mixtures thereof. 18-21. (canceled)
 22. A composition comprising aterpolymer having the structure:

wherein: R₁ and R₄ are independently selected from the group consistingof hydrogen, methyl, and combinations thereof, R₂ and R₃ areindependently selected C1-C20 alkyl, R₅ is selected from the groupconsisting of functionalized and unfunctionalized alkyl, alkoxy,cycloalkyl, alkenyl, and aryl, R₆ and R₇ are selected from the groupconsisting of functionalized and unfunctionalized alkyl, alkoxy,cycloalkyl, alkenyl, and aryl, and wherein R₆ and R₇ may form a 5 to7-membered ring, Q is selected from the group consisting offunctionalized and unfunctionalized alkylene, alkyleneoxy,cycloalkylene, alkenylene, and arylene, X is O, NH, or combinationsthereof, and a, b, and c are molar ratios equaling 100%.
 23. Thecomposition according to claim 22 that is a nutrition, food, beverage,pharmaceutical, cleaning, coating, paint, biocide, construction, energy,industrial, oilfield, personal care, household, performance,agricultural, pesticide, veterinary, fuel, lubricant, adhesive,electronic, textile, ink, or membrane composition.
 24. The compositionaccording to claim 23, wherein said personal care composition is a skinlotion, skin creme, skin ointment, skin salve, anti-aging creme,moisturizer, deodorant, tanning agent, sun block, sunscreen, foundation,concealer, eyebrow pencil, eye shadow, eye liner, mascara, rouge,finishing powder, lipstick, lip gloss, nail polish, make-up remover,nail polish remover, shampoo, rinse-off conditioner, leave-onconditioner, hair styling gel, hair mousse, hair spray, styling aide,hair color, or hair color remover.
 25. The composition according toclaim 22, wherein the terpolymer exhibits antimicrobial activity againsta microbe selected from the group consisting of S. aureus, E. coli, P.aeruginosa, A. niger, C. albicans, and mixtures thereof.
 26. (canceled)27. A method of providing antimicrobial activity, said method comprisingthe step: contacting a composition with at least one terpolymer havingthe structure:

wherein: R₁ and R₄ are independently selected from the group consistingof hydrogen, methyl, and combinations thereof, R₂ and R₃ areindependently selected C1-C20 alkyl, R₅ is selected from the groupconsisting of functionalized and unfunctionalized alkyl, alkoxy,cycloalkyl, alkenyl, and aryl, R₆ and R₇ are selected from the groupconsisting of functionalized and unfunctionalized alkyl, alkoxy,cycloalkyl, alkenyl, and aryl, and wherein R₆ and R₇ may form a 5 to7-membered ring, Q is selected from the group consisting offunctionalized and unfunctionalized alkylene, alkyleneoxy,cycloalkylene, alkenylene, and arylene, X is O, NH, or combinationsthereof, and a, b, and c are molar ratios equaling 100%.
 28. The methodaccording to claim 27 that provides antimicrobial activity against amicrobe selected from the group consisting of S. aureus, E. coli, P.aeruginosa, A. niger, C. albicans, and combinations thereof.
 29. Theterpolymer according to claim 14 wherein said Q is C2-C20 alkylene. 30.The composition according to claim 22 wherein in the terpolymer said Qis C2-C20 alkylene.
 31. The method according to claim 27 wherein in theterpolymer said Q is C2-C20 alkylene.
 32. The terpolymer according toclaim 14 wherein said R₅ is C1-C20 alkyl.
 33. The composition accordingto claim 22 wherein in the terpolymer said R₅ is C1-C20 alkyl.
 34. Themethod according to claim 27 wherein in the terpolymer said R₅ is C1-C20alkyl.